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Why did you choose this product?
Great chair and good price for what you get. Was easy to order on site and delivery was in good time and as shown on tracking. No problems putting together as comes in two parts...
Rotunda Bonded Leather Brown Reclining Chair
Complete your living area with this leather recliner chair. A mix of pure comfort and sophistication, this recliner is upholstered in brown bounded leather and polyurethane, and takes comfort to the next level with the ability to fully recline.
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ITEM#: 14155747Give your home a new look with this awesome brown recliner. This stylish chair features a durable bonded leather and polyurethane upholstery for lasting comfort. The Rotunda Bonded Leather Brown Reclining Chair comes with an attached footrest and features all the way reclining. Relax in this chair with your feet and back fully supported ergonomically. Constructed with a sturdy wood frame, the Rotunda Bonded Leather Brown Reclining Chair has plush foam filling made for lasting comfort.
- Materials: Bonded Leather, Wood, Polyurethane
- Finish: Brown
- Upholstery materials: Bonded Leather, Polyurethane
- Upholstery color: Brown
- Upholstery fill: Plush Form
- All the way reclining
- Seat dimensions: 20 inches high x 23 inches wide x 23 inches deep
- Dimensions: 36 inches high x 39.5 inches wide x 37 inches deep
Assembly required
Avoid placing your furniture in direct sunlight and maintain at least two feet between furniture and heat sources. Aniline and Protected leathers are especially sensitive to direct sunlight. Use a professional cleaner to help resist staining and prevent overall soiling.
|Bonded Leather Leather Wood
|Chair Type
|Assembly Required
|Furniture Frame Material
|Furniture Pattern
|See description
|Bonded Leather, Polyurethane
|Model Number
Customer Reviews
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leather reclining chair
Great chair and good price for what you get. Was easy to order on site and delivery was in good time and as shown on tracking. No problems putting together as comes in two partsRead More
I have not opened the crate.
I know now that you have to explain everything to a person at the other end of the phone, ask a lot of questions and hope you receive the right answers. All the people I spoke to were excellent. But I told them my age, disabled, they should of told me that I had to put the recliner together, or try and sell me one that was. Also your free delivery was with ups and or fedex are not allowed to deliver parcels into a home or apartment. They would leave it outside. In bad weather we would of had a problem. In closing I will say that in the future I might purchase something from overstock.Read More
Rotunda recliner
The foot rest is hard to push in. Wish it was a rocker also.Read More
Rotunda Bonded Leather Brown Reclining Chair
Great chair, super comfortable. If you are short this chair is great for you. So many chairs the head rest hits in the wrong spot and is very uncomfortable for my neck. This chair is perfect, fits just right and reclines easily.Read More
The chair arrived and was unpacked and assembled. Upon sitting down and putting the chair into recliner position, it locked and would not return to upright position. This made it very difficult to get out of. It was returned easily and a refund sent.Read More
"Sits" like a glove
We got this for our 4 year old who has asthma so she can get some rest. The arms are like pillows and low so she's comfortable lying in it. The chair is super comfortable. Soft, yet firm. My complaint is the frame work seems wobbly and I'm betting on problems down the line, but we bought the warranty so when that happens we'll just replace it! Overall I like the chair, but more importantly our daughter likes it and it works great for her.Read More
Questions & Answers
I liked the chair and the price
Is the control for reclining really located on the left side of the chair as shown in the picture?
Hello jhep5733, on the Rotunda Bonded Leather Brown Reclining Chair the control is really on the left and right side. Please feel free to contact us again with any further questions. Thank you for shopping with us!
on right side as all other reclining chairs owned
How dificult is the assembly?
Thank you for shopping with us cms0424. This will be very easy to assemble. It will either require the back to be attached to the seat or the arms and back to be attached to the seat. Have a great day.
assembly very easy and instruction with it also
Can you raise the leg and continue to sit upright?
Yes you can.
Will this support a 300lb person in comfort?
The unit can hold the weight whether in comfort is up to the person.
What is the weight capacity?
Thank you for your interest. We are currently looking into this. Your answer will be posted in 1 to 2 business days.
What are the inside seat dimensions? What is the warranty on this v
This item does not come with a warranty, but you may purchase a 5-year warranty from us. The seat dimensions are 20 inches high x 23 inches wide x 23 inches deep.
Does it also a rocking chair?
No, it does not rock.
What type of assembly is required?
The item comes in several pieces that you must put together.
Shopping Guides
How to Clean a Leather Recliner
Whether it's in your living room or in the man cave, your leather recliner needs to get cleaned now and then. If it's Dad's favorite spot to watch the game -- and eat snacks at halftime -- then it probably even needs regular deep cleaning. Fortunately, cleaning a leather reclining chair is surprisingly easy. You'll be able to make your leather furniture feel fresh and clean in no time.
FAQs about Recliners
Add a comfortable recliner to your living room, and you'll always have the perfect place to relax. If you aren't sure if a recliner chair is right for your home, or if you aren't sure which one to choose, let the answers to these frequently asked questions about recliners help guide you.
Recliner Buying Guide
Recliners are a man's domain, or so they say, but with the multitude of stylish options available, recliners have become just about everyone's favorite chair. There are a lot of recliners available to consumers today. The choices seem endless, but when searching for a recliner, you'll want to consider how it will fit in your room and blend with your furniture as well as who will be using it the most. Find the perfect recliner with this recliner buying guide, which will show you how to buy recliners that will help you relax for years to come.
How to Pick a Recliner
Adding a comfortable and stylish recliner in your living room is an excellent way to update your home's decor. Recliners are popular because of the incredible comfort they offer. For many people, choosing a recliner and other chairs for the living room or family room is more important than choosing any other piece of furniture. A recliner is where you really want to relax at the end of a day, so it's important to choose the right one for you. There is a wide range of styles, fabrics and options to choose from when picking a recliner, so take your time and carefully choose the perfect chair that will keep you happy and relaxed for a long time. Keep reading for steps on how to pick a recliner.
How to Measure a Recliner for a Slipcover
Whether you want to update an old chair or protect a new one from spills and stains, a recliner slipcover will do the job. Should something spill on the slipcover, you can easily clean it, as most are machine washable. Slipcovers let you change the color of a recliner to match any decor, too. Before you buy a slipcover, however, you'll need to measure your reclining chair to ensure a proper fit. These steps for measuring work for recliners with either attached or separate footrests.
Easy Chairs Fact Sheet
Any overstuffed recliner or comfortable padded chair may be referred to as an easy chair. These cozy chairs, usually laden with features, are designed for relaxation. Often used in living rooms, dens or recreation rooms, easy chairs and recliners are the perfect spot to unwind with a good book or watch a movie. Take a look at the easy chairs fact sheet below to learn more about these cozy pieces of furniture.
How to Choose a Chaise Lounge
When you're ready to relax in your own living room, it's time to consider a chaise lounge. A chaise lounge is a long chair designed to support your head and legs while you recline. A traditional lounge chair has either a low back that runs the length of the chair or no back at all. Looking almost like a modified sofa, a chaise lounge is best used for a single, reclining person, but it can accommodate several people sitting upright. How do you choose the chaise lounge that's right for you? Read on to find out.
Tips on Making Leather Furniture Last
Leather furniture is a wise investment that pays off in style, class and comfort. Leather furniture can range from leather sofas and loveseats to ottomans and recliners. Your new leather furniture will beautify your home quickly. Regrettably, if it's not maintained, leather furniture can age quickly. Your furniture can go from terrific to tacky in a matter of years if it doesn't receive the proper care. Fortunately, there are some easy tips on making leather furniture last that are simple and effective.
Best Locations for Chaise Lounge Chairs
If you're looking for unique, statement-making furniture, why not purchase chaise lounge chairs for your home? With their distinctive reclining frame and length, chaise lounges can add style to your decor both inside and out. Read on to discover the best locations for chaise lounge chairs.
How to Buy a Reclining Sofa
A reclining sofa brings the best of two worlds together: the comfort of a recliner and the size of a sofa or loveseat. Before you buy a reclining sofa, there are a few things to keep in mind that will make your purchase easier and ensure that you are more than pleased with your new piece of furniture.
How to Buy Slipcovers
One of the simplest ways to update your decor is to buy slipcovers. Available in many sizes to fit chairs, futons, sofas, sectionals and even recliners, furniture slipcovers can be an easy solution when you're redecorating on a budget. Choosing quality sofa and chair slipcovers will be less expensive than replacing your old furniture, especially if the item is sturdy and comfortable, and a well-fitting chair or sofa slipcover will complement your room and give your furniture a face-lift. Whether you need to cover up old couches that have seen better days with sofa slipcovers or just want a fitted slipcover to give your armchair a fresh, polished look, the following suggestions will help you find the perfect furniture covers for your home. Read on for tips on buying slipcovers.
Trends in Leather Necklaces
Leather has always been trendy, and leather necklaces are a current hot item. Leather necklaces are very hip in men's jewelry categories because they are masculine, edgy and nature-inspired. Whether you choose black leather jewelry, brown leather men's necklaces or dyed leather necklaces, leather jewelry is versatile and always unique. You can add leather necklaces to any basic outfit to punch up the style; check out the top trends in leather men's necklaces before you start shopping.
How to Care for Leather Chair Seats
From office chairs to kitchen and dining room chairs, leather seating is beautiful and can maintain its beauty for a long time if cared for properly. All chair seats are subjected to food crumbs, food and drink spills and even perspiration. Removing these substances, especially liquid spills, from leather chairs is essential to prevent fading and damage to the leather. Cleaning and maintaining leather furniture rarely takes much time, if done regularly, and can protect your chairs and other leather furniture for many years.
How to Find Great Cheap Leather Chairs
Leather furniture adds a rich and comfortable atmosphere to any room, but leather can be expensive. While there are leather chairs that are $500 and up, it is possible to find high-quality, beautiful leather chairs for under $200. If you'd like a leather chair but you don't want to spend a lot of money, you'll just need to consider a few factors before you start shopping to make sure your affordable leather chair is a good choice for your home.
Leather Chair Care
It's no surprise that leather chairs reside at the center of home style and fashion. These beautiful chairs are comfortable and look fabulous in any home. You usually see a leather chair sitting in a living room or library, and -- just like any other piece of furniture -- they need regular maintenance. Performing necessary leather chair care should be done on a regular basis. If you care for your leather furniture, it will reward you with many years of quality service.
Best Rooms to Furnish with Leather Chairs
Adding a few leather chairs to any room instantly introduces an aura of sophistication and comfort. For thousands of years, leather has been used for furniture and other dependable items because it is both durable and attractive. Although you can't go wrong with quality leather chairs in any room, some rooms in your home shouldn't go without one or two.
Tips on Decorating with Leather Chairs
Leather furniture is prized for its many qualities, including but not limited to, durability, attractiveness and luxurious style. When you're ready for your living room furniture to speak volumes, then you're ready to look into leather chairs. For tips on decorating with leather chairs, read on and get ready to make your living room, dining room, drawing room or den the most inviting room in your home.
How to Care for Living Room Chairs
Whether your living room chairs are upholstered in leather, fabric, or microfiber, they will require some care. Each type of material has different needs. Here are a few maintenance tips to ensure your chairs will last for many years.
Why You Need an Outdoor Chaise Lounge
Summer is all about soaking up the sun, and the perfect patio set-up is not complete without a relaxing outdoor chaise lounge. Long enough to use as a head-to-toe recliner, the chaise lounge is the ultimate patio indulgence. Not convinced? This guide is sure to show you that an outdoor chaise lounge is a necessity.
How to Maintain a Leather Sofa
If you are planning to buy a leather sofa, you'll want to make sure you know how to maintain the upholstery. A leather sofa can be one of the most comfortable and stylish pieces of furniture in your home. Whether you are considering a leather sectional sofa, sleeper sofa, leather chairs, or any other piece of leather furniture, you can significantly extend their longevity by giving them proper and consistent care. Here are a few tips to make sure your leather sofa will be a favorite furniture piece for years.
Shipping & Returns
Usually leaves our warehouse in 1-2 business days. *
Standard Return Policy:
Items must be returned in new or unused condition and contain all original materials included with the shipment. More Details
FINAL SALE EXCLUSION: Items marked as FINAL SALE are not returnable unless the problem you experience is the result of our error.
This item cannot be shipped to Alaska or Hawaii. More details
Shipping Information:
Our standard shipping method is ground shipping. We also offer expedited shipping for most items. Your final
shipping cost and estimated delivery timeframe will be available at checkout.
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* For your protection, all orders are screened for security purposes. If your order is selected for review, our Loss Prevention Team may contact you by phone or email. There may be a two business day delay to process your order.
** Most Oversize orders are delivered within 1-4 weeks. Some orders may take 6 weeks to be delivered.


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Waiting to shop?
Hi, I am Samantha. Married to Chris. Mommy to Nolan.
Expecting Baby #2 November 28, 2014!
Clomid (50mg) Round 2 = BFP!!!
Nope, I'm going to wait until we find out sex at 21 weeks. We don't need too much though.
Blogging about the life of a SAHM, from cooking and cleaning to budgeting, gardening, crafting and more.
PPROM Queen.
DD1 is R.I.O. 12/01/2011 (28w6d preemie)
DD2 is Z.O.O. 11/01/2014
We have a ton of very recent stuff from my 10 month old boy - and it's another boy, so we are pretty set to do it all over again. :-)
I am going to splurge and buy myself something I've wanted since I had him - a Tula carrier. We had a Bjorn for this one but as soon as he was over about ....15 lbs or so, it hurt my back. So, I plan on treating myself and ordering one this week. I'm a super-thrifty type, so for me, it's a pretty big indulgence. :D
I think I'd really like a nice glider this time, too.....
i'm waiting until 3rd tri.
Helen Marie: RIP, 22.4 wks, 9.11.13, incompetent cervix
Our rainbow baby boy is here! Anton Justin born 10.27.14. Ask me anything about IC.
Dan(22) + Eden(22) = Ellaina Annabel-lee (8/9/12) & Raven Lucille (12/2/14)

subset: commoncrawl


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Credits & Info
- Date
- 05/12/2004
- File Info
- Song
- 2 min 0 sec
- Score
- 4.34 / 5.00
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Rated 2.5 / 5 stars
Har har har! My little sister (8 yrs.) wont stop laughing at the dumb song. This could be played with the credits of a comedy short, or on some blooper scenes. I dunno.
Rated 2.5 / 5 stars
I dont know what you was smokeing but i surly want some cuz this song is Wacked BIG TIME....
Rated 5 / 5 stars
I dont even care...
I dont even care about the rating, its AWESOME! I sweatr,, while watching Futureama, on Adult Swim, its on there, so you MIGHT hacve gotten it from there, or sumthin on Futurama, anyways, this is weird, and it IS nonsense
Rated 5 / 5 stars
i was lookin through the audios today and stumblaed across this. it's probably the best one on here although there's no point to it. i downloaded it from the site and tried to burn it but it wasn't compadible with the media player... it's just too bad i can't enjoy it anywhere but at my computer... anyway good job perfect 10!!!!!!!!!
Rated 5 / 5 stars
That was the best song ever!!!!!
I listen to it basicly everyday!!!!!!
You're my hero


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Buchanan Hotel
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Historical Traveler Reviews Buchanan Hotel Glasgow
Nice city shame about the hotel!
I do not like writing negative things about places but if I am honest, I would NEVER stay here again. Firstly, on arrival I was put in a room with floor boards that moved and electrics that must have been installed by a blind man! After the receptionist phoned me to say there was a problem with the room (did she know to start with) I was moved to another room which was slightly better. However, regardless of the room you have you will both hear and feel the tube trains as the hotel is smack bag over the tube line. Don't plan on sleeping as if the tubes don't keep you awake, the noise from the street will as its in a busy high street.
One final point that put me off was finding a pest control box behind the wardrobe.
Christmas a real treat
Having read the reviews for the Buchanan we were very worried as we had booked with two other best friends to spend our first Christmas away in 40 years. But our worries were completely unfounded.
Kevin and his Staff could not have done more for us to ensure we all had a brilliant time. The food was excellent throughout with multiple choices for each course at every meal. The rooms were clean, tidy, warm and very comfortable. The entertainment was very good especially the Scottish Band on Boxing Night. We would also like to point out their attention to security which was first class. For retail therapy the good choice of shops is just across the road!! We would recommend this Hotel without reservation and hopefully stay there again sometime in the future. Many thanks to all, Mrs & Mrs J Harper and Mr & Mrs P Davies.
First class food
I stayed in the hotel at new year excellent location and first class meals similar to the standard of food expected in four star delux establishments. My overall impression of the hotel was that the staff try so hard to exceed customer expectations. The rooms were very clean & comfortable. Looking foward to seeing you all next time round.
Great location
Had a superb 2 night stay in this hotel, it is so handy for the shops being smack bang in the city centre. Bedroom was very clean and had everything I needed including bags of hot water. The breakfast was also great - a huge selection of both hot & cold dishes. Would go back anytime. The staff always had a smile on their faces.
Bloody awful
Had the misfortune to stay at this hotel a few weeks ago. Thought it was going to be great due to location. It was for 5 minutes! Realisation set in when we tried to open windows to get some air. Only one window opened but had to be propped up by the Gideon bible, (sorry)!
We then realised that although we had air, we also had lots of noise too! Glasgow is a great city with a wide variety of things to do and see and HEAR!!!
Believe me we heard them all!!!!
The next decision was which of the 3 big scary brown wardrobes, to hang our stuff in! Honestly, these things were the things of childhood nightmares! Who knows what things could be hiding in them, monsters, snakes, former guests!!
I've always wondered what happened to my grandparents stuff when they passed, I now know.
The rooms are dark and small with terrible ensuite facilities. The sink does not drain any water away. Please, if there are 2 of you staying, brush your teeth together 'cos at least you know some of the foam is yours!!
Terrible hotel, stay clear, you have been warned.
A better experience than the other reviewers
I read the first four reviews here with great sadness; I'm genuinely sorry others had such a bad time here, and had I read these reviews before booking my travel I wouldn't have stayed there at all. Fortunately, I didn't, and I actually had an experience quite contrary to the other posters. Yes the rooms are small, but that's true of pretty much every hotel in Europe. It was clean, comfortable and reasonably well-appointed. It wasn't a suite at the Savoy, but then it wasn't intended to be, either.
I found the desk staff, and Kevin in particular, to be very welcoming and friendly, and they were more than willing to pass along advice and suggestions, whether for transport or dinner, and they were spot-on with each. Admittedly, it may have helped that they learned when I checked in that I'm an American coming back to visit his roots (my father emigrated to America in 1927). I thoroughly enjoyed my brief stay.
Who needs sleep anyway!!!
I stayed here with my daughter - thankfully for only one night, otherwise we would have lost the will to live!
It was dirty, smelly, noisy (you name it, it was it!)
There were 4 beds in our room with a spacious 10cm gap between each one.
There was no remote for the TV, but a train horn sounding regularly to keep us awake!
The sink in the bathroom didn't drain properly at all (lovely).
All in all it was a lesson in everything a hotel should not be. My daughter is currently receiving counselling after the experience, I am hoping the nightmares will stop soon!
Do not stay at this place unless you are studying horrible hotels!
Don't stay here!
I was very concerned about staying in this hotel after reading the two previous reviews. However, my husband and I were going to the British Open and all the other hotels in the area were booked. We stayed there July 17-18, 2004. The only reason I went back for a second night was because we couldn't find another hotel. This hotel was the only low point in our otherwise wonderful vacation. It is very dingy. The beds are lumpy and the bathrooms are very old. There is a very loud bar next door that plays music until all hours of the morning and because it is located on a pedestrian mall the people are out partying and yelling until 2-3 in the morning. We had to keep our windows open because we were on the fourth floor and it is very warm up there. The only positive thing I can say about the hotel is that it is in a good location to catch the train. It is just a few minutes walk to Glasgow Central and Glasgow Queen Street Stations.
God Awful
This hotel overbooked my reservation & was totally uninterested in my plight.
With Glasgow very busy they suggested a run down b&b with no -ensuite, no facilities miles out of town.
They didn't care where I slept as long as I got out of their hotel.
Avoid at all costs
Couldn't wait to get out of there!
Awful place. First, it is located on a pedestrian mall, so if you drive you have to park on the street and not remotely close. Bear that in mind if you have lots of luggage that you don't want to leave in the car overnight! Second, even though we called ahead to ensure that we had a double bed, we ended up in a room with three twins. That was after the first room they gave us that already had someone staying in it! Third, despite how nice it looks on the website/brochure, it was REALLY shabby/grimey - could easily be a flophouse. Fourth, it's one door down from a very loud 24 hour karaoke bar with bright neon signs!
Honestly, we couldn't leave early enough the next morning, even skipping our included breakfast. This place was the low point in an otherwise wonderful UK vacation.
TripAdvisor Reviews Buchanan Hotel Glasgow
Travel Blogs from Glasgow
Scotland & Ireland & traveling friends
... I have connected with fellow travellers to the level where it feels like we have been friends for years! While constantly saying goodbye to friends you make can be extremely hard, knowing that you may perhaps run into them again in another city or even realising that fact you know people from all over the world counterbalances this feeling.
So in saying this I actually extended my initial travel plans by 5 weeks so I could spend more time traveling around the UK catching up ...
Weekend in Glasgow
... 8211; Buchanan St, found our hostel on the river (it was quite a nice place actually), checked in, freshened up and headed back out to join the rest of the town. Beer gardens looked like the places to be, sitting out in the sun with a cider was just what we had in mind. After walking around to check out what was on offer we got a table as a busy outside bar and yet again ate another pizza….we vowed that this would be the last pizza for the trip ...
Glasgow, Scotland
... that there is a lot of deep fried things in Scotland and we already knew about the famous deep fried mars bar but the concept of the pizza was a bit strange. The comedy show we went to was at a small establishment for stand up comedians. There were 5 acts, 3 were good and two were a bit strange. It wasn't as good as Nz comedy however the MC Billy Kirkland was hilarious, he was a typical Scottish man which made him even more ...
Forth again
... home it would have dried on his legs and he got "hammered". The masonic lodge was important among the workers and they used to meet at an old building that still stands on the mine site. To this day once a year the freemasons march from Forth (where they have a conspicuous building) and walk three times around the old building. Later he gave me a history of the local lodge, including Somerville names, which also mentioned this annual walk. ...
Breasclete day 11-From Iron Age to Stripping
... you should google it.
Twyla, you asked if I met anyone famous. Yes, I did. Anne excitedly dragged me over to meet Adam Henson. Earlier I had heard a woman swooning because Mr. 'Handsome' had kissed her on the lips. I was about to meet him. He was short, with curly red hair and probably looked handsomer later in the evening than earlier. As we shook hands, I said, I hear you are somebody famous, to which he replied, no, I am just an ordinary bloke. Apparently he was a ...


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Kinetic determination of morphine by means of Bray-Liebhafsky oscillatory reaction system using analyte pulse perturbation technique.
ABSTRACT A novel kinetic method for micro-quantitative determinations of morphine (MH) is proposed and validated. The method is based on the potentiometric monitoring of the concentration perturbations of the oscillatory reaction system being in a stable non-equilibrium stationary state close to the bifurcation point between stable and oscillatory state. The response of the Bray-Liebhafsky (BL) oscillatory reaction as a matrix system, to the perturbations by different concentrations of morphine, is followed by a Pt-electrode. The proposed method relies on the linear relationship between maximal potential shift, DeltaE(m), and the logarithm of the added morphine amounts in the range of 0.004-0.18 micromol. Under optimum conditions, the sensitivity of the proposed method (as the limit of detection) is 0.001 micromol and the method is featured by good precision (R.S.D.=1.6%) as well as the excellent sample throughput (45 samples h(-1)). In addition to standard solution analysis, this approach was successfully applied for quantitative determination of morphine in a typical pharmaceutical dosage form. Some aspects of the possible mechanism of morphine action on the BL oscillating chemical system are discussed in detail.
Article: Rapid and simple electrochemical detection of morphine on graphene-palladium-hybrid-modified glassy carbon electrode.[Show abstract] [Hide abstract]
ABSTRACT: A hybrid of reduced graphene oxide-palladium (RGO-Pd) nano- to submicron-scale particles was simultaneously chemically prepared using microwave irradiation. The electrochemical investigation of the resulting hybrid was achieved using cyclic voltammetry and differential pulse voltammetry. RGO-Pd had a higher current response than unmodified RGO toward the oxidation of morphine. Several factors that can affect the electrochemical response were studied, including accumulation time and potential, Pd loading, scan rate, and pH of electrolyte. At the optimum conditions, the concentration of morphine was determined using differential pulse voltammetry in a linear range from 0.34 to 12 μmol L(-1) and from 14 to 100 μmol L(-1), with detection limits of 12.95 nmol L(-1) for the first range. The electrode had high sensitivity toward morphine oxidation in the presence of dopamine (DA) and of the interference compounds ascorbic acid (AA) and uric acid (UA). Electrochemical determination of morphine in a spiked urine sample was performed, and a low detection limit was obtained. Validation conditions including reproducibility, sensitivity, and recovery were evaluated successfully in the determination of morphine in diluted human urine.Analytical and Bioanalytical Chemistry 07/2014; · 3.66 Impact Factor
Article: Entropy production in the Oregonator model perturbed in a calorimeter with a chemical pulse[Show abstract] [Hide abstract]
ABSTRACT: The classical Oregonator model of the Belou- sov–Zhabotinsky reaction is used to examine the response of an oscillating reaction to a chemical perturbation in a batch calorimeter. To do this, a reaction step for the per- turbing chemical substance and the energy balance equa- tion are added to the model. Changes in the frequency and amplitude of the oscillations occur as a function of the concentration of the perturbing substance, and these changes are quantified by applying the thermodynamics of irreversible processes in order to determine the rate of entropy production. Various criteria are proposed to eval- uate the time series and measurable quantities with linear correlations between the entropy production due to transfer and the concentration of the chemical perturbation are obtained, showing that it is possible to implement experi- mental protocols in the proposed methodology.Journal of Thermal Analysis and Calorimetry 09/2014; 119(1). · 2.21 Impact Factor
- [Show abstract] [Hide abstract]
ABSTRACT: Oscillating chemical reactions, which are far from equilibrium, are extremely sensitive to certain species and may provide new analytical methods using the regular oscillations as well as the non-equilibrium stationary state after system bifurcation. This review of their application to analytical chemistry from 2005 to 2012 includes other appropriate references. Both organic and inorganic analytes are included.Central European Journal of Chemistry 07/2013; 11(7). · 1.33 Impact Factor
Page 1
Analytica Chimica Acta 582 (2007) 367–374
Kinetic determination of morphine by means of Bray–Liebhafsky
oscillatory reaction system using analyte pulse perturbation technique
Nataˇ sa D. Peji´ ca,∗, Slavica M. Blagojevi´ ca,1, Slobodan R. Ani´ cb,1, Vladana B. Vukojevi´ cf,1,
Miroslav D. Mijatovi´ cc, Jasna S.´Ciri´ cc, Zoran S. Markovi´ cd,
Svetlana D. Markovi´ ce, Ljiljana Z. Kolar-Ani´ cb,1
aFaculty of Pharmacy, Department of Physical Chemistry, University of Belgrade, Vojvode Stepe 450, YU-11000 Belgrade, Serbia and Montenegro
bFaculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, P.O. Box 137, YU-11001 Belgrade, Serbia and Montenegro
cMinisty of Interior Administration of Police Forensic Science, Kneza Milosa 103, YU-11001 Belgrade, Serbia and Montenegro
dFaculty of Agronomy, University of Kragujevac, 34 Cara Duˇ sana, YU-32000ˇCaˇ cak, Serbia and Montenegro
eFaculty of Science, University of Kragujevac, 12 Radoja Domanovi´ ca, POB 60, YU-34000 Kragujevac, Serbia and Montenegro
fDepartment of Clinical Neuroscience, Karolinska Institute, CMM L8:01, 17176 Stockholm, Sweden
Received 23 June 2006; received in revised form 3 September 2006; accepted 14 September 2006
Available online 19 September 2006
A novel kinetic method for micro-quantitative determinations of morphine (MH) is proposed and validated. The method is based on the
potentiometric monitoring of the concentration perturbations of the oscillatory reaction system being in a stable non-equilibrium stationary state
close to the bifurcation point between stable and oscillatory state. The response of the Bray–Liebhafsky (BL) oscillatory reaction as a matrix
system, to the perturbations by different concentrations of morphine, is followed by a Pt-electrode. The proposed method relies on the linear
relationship between maximal potential shift, ?Em, and the logarithm of the added morphine amounts in the range of 0.004–0.18?mol. Under
optimum conditions, the sensitivity of the proposed method (as the limit of detection) is 0.001?mol and the method is featured by good precision
applied for quantitative determination of morphine in a typical pharmaceutical dosage form. Some aspects of the possible mechanism of morphine
action on the BL oscillating chemical system are discussed in detail.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Morphine; Bray–Liebhafsky reaction; Quantitative analysis; Analyte pulse perturbation; Kinetic method
1. Introduction
Oscillatory chemical reactions realized in closed or open
reactors exhibit different dynamic behavior such as stable non-
lations or chaotic dynamics, depending on the values of the
control parameters such as temperature, initial concentrations
of the reactants or specific flow rate [1–7]. Being subjected to
controlled perturbations, certain dynamic states exhibit extreme
sensitivity. This feature can be exploited for quantitative anal-
∗Corresponding author. Tel.: +381 11 3130678; fax: +381 11 3130678.
E-mail address: email@example.com (N.D. Peji´ c).
1These authors contributed equally to this study.
ysis and was extensively examined in the Bray–Liebhafsky
From the first report by Tichonova et al. [17], numerous analyti-
reactors were developed and the advantage of applying oscilla-
tory chemical reactions in quantitative analysis were elaborated
by Jim´ enez-Prieto et al. [18] and Gao [19]. So far, two distinct
methods were proposed. The method described in [20] is based
changes in both the amplitude and the period of the oscillations
that were proportional to the concentration of the analytes. The
satisfies the requirements of most determinations [18,19]. On
0003-2670/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
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N.D. Peji´ c et al. / Analytica Chimica Acta 582 (2007) 367–374
the other hand, the perturbation technique proposed in [21–25]
relies on perturbing the Bray–Liebhafsky reaction system being
in a stable stationary state in the vicinity of a bifurcation point.
The above mentioned methods based on different oscillatory
chemical systems have been successfully applied to determin-
ing several species in purified samples and laboratory mixtures,
but were also applied to more complex samples derived from
pharmaceutical dosage forms or commercially available bever-
ages [18–25].
for quantitative determination of morphine by perturbing a sta-
ble stationary state that is found in the vicinity of a bifurcation
point in the BL reaction matrix, in order to minimize the time of
analysis without loosing the precision and accuracy. The selec-
tion of the BL reaction as the matrix results from our profound
understanding of its mechanism [11–15] and previous positive
experience [21–25]. By perturbing the matrix system being in
a stable stationary state it is not necessary to test the oscilla-
tory phases and select always the same oscillatory phase point
for perturbation, which is experimentally delicate and time con-
For practical applications, it is not required to understand the
mechanism of interaction of the analyte with the matrix system.
tion and the chemistry of the compound that is to be analyzed
in order to assess in advance whether this approach is feasible,
at all, for that particular compound. Therefore, we discuss pos-
sible interactions between morphine and the BL matrix and we
have performed numerical simulations to test the validity of our
1.1. The Bray–Liebhafsky reaction
The apparently simple catalytic decomposition of hydrogen
peroxide in the presence of hydrogen and iodate ions (D):
known as the BL oscillating reaction, is a net result of two main
kinetic pathways:
The reduction of iodate to iodine (R):
and its subsequent oxidation back to iodate (O):
The (R) and (O) pathways consist of numerous elementary
steps during which iodine-containing intermediates such as I−,
I2, HIO and HIO2 are being formed and decomposed. The
elementary steps are intertwined and form a complex self-
regulating network of molecular interactions [11–13,26–31].
equilibrium, the BL reaction exhibits self-organized tempo-
ral dynamic structures typical for non-linear systems including
non-equilibrium stationary states, simple periodic oscillations,
complex oscillations, bursts and deterministic chaos [32–34].
Fig. 1. Structure of morphine.
2. Experimental
2.1. Chemicals and reagents
acid and ethanol were obtained from Merck (Darmstadt, Ger-
many) and hydrogen peroxide from Fluka (Buchs, Steinheim,
Switzerland). The structure of morphine is shown in Fig. 1.
(ρ=18M?cm, Milli-Q, Millipore, Bedford, MA, USA) was
used. Standard stock solutions of morphine were prepared at
the concentration of 4.6×10−2M in ethanol (Merck, Darm-
stadt, Germany) and were stored in refrigerator, in the dark.
Prior to injection, stock solutions were appropriately diluted
with ethanol before being used as working solutions.
2.2. Apparatus
The BL reaction was conduced in a continuously fed well
rounded by thermostating jacket (M 876-20, Metrohm, Herisau,
Switzerland) was used as a reaction vessel. The temperature of
bath (Series U8, MLW, Freital, Germany). A magnetic stirrer
(IKA-COMBIMAG RET, Staufen, Germany) was used to stir
continuously the reaction mixture. The flows of the reactants
through the reaction vessel were driven by peristaltic pumps
(Ole Dich Instrumentmakers, Hvidovre, Denmark). Viton tubes
(Deutch & Neuman, Berlin, Germany) were used to transport
the aqueous solutions of potassium iodate and sulfuric acid
were used for hydrogen peroxide. These tubes were connected
to Teflon tubes (Varian, Darmstadt, Germany), and the reagents
iments, the feeding solutions were kept in reservoirs, at room
temperature, and were introduced into the reaction vessel sepa-
rately. The volume of the reaction mixture was kept constant at
V=22.2±0.2mL by removing the surplus volume of the reac-
tion mixture through the U-shaped glass tube.
Temporal evolution of the system was monitored potentio-
metrically (MA 5730 potentiometer, Iskra, Hojrul, Slovenia)
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N.D. Peji´ c et al. / Analytica Chimica Acta 582 (2007) 367–374
using a Pt electrode (Model 6.0301.100, Metrohm, Herisau,
Switzerland) versus a double junction Ag/AgCl electrode
(Model 6.0726.100, Metrohm, Herisau, Switzerland) as a refer-
ence. In the reference Ag/AgCl electrode, the inner electrolyte
was a 3M KCl and the outer electrolyte was a saturated solution
(Servogor 220, BBC Goerz, Nuenen, Austria).
Perturbation of the BL matrix was performed by manual
injections. The analyte was introduced using micropipettes
(Brand, Wertheim, Germany). A 50?L shot is estimated to
last about 0.5s. Intensity of the perturbation corresponds to
the total amount of morphine in the 50?L aliquot of standard
2.3. Procedures for determination of morphine
tionary states were evaluated for quantitative determination of
morphine. To reach the appropriate dynamic state the following
start-up procedures were applied.
2.3.1. Procedure A
Fifteen millilitres of [KIO3]=1.5×10−1M and 7.5mL of
[H2SO4]=2.4×10−1M were introduced into a pre-warmed
of 900rpm for 50min. Then, 7.5mL of [H2O2]=2.8×10−2M
was added to this mixture and shortly afterwards, oscillatory
evolution of the BL reaction was observed. The reaction was
driven in a bath mode until the transient oscillations disap-
peared and monotonic evolution was observed. Only then,
approximately 120min after the addition of hydrogen per-
oxide, the inflows were turned on at the required flow rate
(j0=4.48×10−3min−1), and temperature was adjusted to the
working value, T=35.0, 37.0 or 39.0◦C. The mixed inflow
concentrations of the reactants were [KIO3]0=7.5×10−2M,
[H2SO4]0=6.0×10−2M and [H2O2]0=7.0×10−3M. This
preparatory procedure, described in detail in [23], takes about
2.3.2. Procedure B
About 45mL of reaction mixture was introduced into
a reaction vessel that was pre-warmed (water bath set at
T=60.0◦C) and shielded from light, using the three sepa-
rate inflows at maximal flow rate (the total volume flow was
12mLmin−1). In this way the following mixed inflow concen-
[H2SO4]0=5.5×10−2M and [H2O2]0=2.0×10−1M. The
inflows were then stopped and the stirring turned on at
r=900rpm. The excess of the reaction mixture was sucked-out
through the U-shaped glass tube until the actual reaction mix-
ture volume, V=22.2±0.2mL was reached. Thus, the reaction
starts in a bath mode and after two transient bath oscillations
(after about 30min) the inflows were turned on at the required
specific flow rate, j0=2.95×10−2min−1and the temperature
was adjusted to T=30.0, 33.0, 40 or 42.9◦C. This prepara-
tory procedure takes about 1h and is described in detail in
2.3.3. Procedure C
The preparatory procedure is similar to the one described
in B except that higher stirring rate, r=1200rpm, and dif-
ferent mixed inflow concentrations, [KIO3]0=4.74×10−2M,
[H2SO4]0=4.79×10−2M and [H2O2]0=1.55×10−1M, are
used. Under these conditions, after two bath transient oscil-
lations (after about 40min), the specific flow rate was
adjusted to one of the examined values j0=2.52×10−2min−1,
2.80×10−2min−1, 4.90×10−2min−1or 7.00×10−2min−1
and, if necessary, the temperature is readjusted to T=60.0◦C.
This preparatory procedure takes about 1h.
3. Results and discussion
3.1. Optimization of the experimental conditions
control parameter (temperature or specific flow rate), i.e. bifur-
cation analysis, has to be preformed before the actual analysis.
This procedure is applied to locate the actual position of the
bifurcation point in the parameter phase space, which may vary
slightly for different set-ups in different laboratories. However,
cases denoted by A, B and C are presented in Fig. 2.
Under the experimental conditions A and B, we examined
the dynamics of the matrix system by varying the tempera-
ture from 30.0 to 60.0◦C, while the other parameters (specific
flow rate and mixed inflow concentration of the fed substances)
ing the envelope of the simple periodic oscillations for T≥42.0
and 44.6◦C (experimental conditions A and B, respectively),
as well as the locus of the stable non-equilibrium stationary
state (35.0≤T≤41.8◦C and 30.0≤T≤43.3◦C, for experi-
mental conditions A and B, respectively), give the bifurcation
points at the temperatures where dynamic regimes are changed
(Fig. 2(a) and (b)). In the case A, the bifurcation point is
found at TBP,A=41.9◦C, whereas in the case B it is found
at TBP,B=43.2◦C. The bifurcation points are found by linear
extrapolation of a plot of the square of the amplitude of the limit
cycle oscillations versus temperature.
Under the experimental conditions C, the dynamics of the
matrix system was examined by varying the specific flow rate
from 5.0×10−4to 1.26×10−1min−1, while the other parame-
stances) remained unchanged. The bifurcation diagram, show-
ing the envelope of the simple periodic oscillations (for spe-
cific flow rate between 1.11×10−3≤j0≤1.95×10−2min−1)
and two distinct stable stationary states characterized by
higher and lower potential values of the stable non-equilibrium
stationary states (for the respective intervals of specific
flow rates: 5.0×10−4≤j0≤7.0×10−4min−1and 2.52×
10−2≤j0≤1.26×10−1min−1) is presented in (Fig. 2(c)). The
lower bifurcation point is found at j0=1.04×10−3min−1, and
the higher one at j0=2.38×10−2min−1. In these two cases, the
arithm of the distance between the considered j0and the critical
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N.D. Peji´ c et al. / Analytica Chimica Acta 582 (2007) 367–374
Fig. 2. Bifurcation diagrams showing transition from the stable stationary state
(solid circles) to the sustained periodic oscillations (open circles) that denote
minimal and maximal potential in an oscillation obtained in experimental pro-
cedures A (a), B (b) and C (c). The operations points are indicated by arrows.
value of j0kversus the average period between the oscillations
As can be seen from Fig. 2, different dynamic states can be
achieved in the examined parameter phase space depending on
the initial conditions. We have chosen to perform perturbations
only in the stable non-equilibrium stationary states. Therefore,
around each bifurcation point we analyzed several stable sta-
tionary states, indicated by arrows in Fig. 2, and tested their
turbed the stationary states that are realized at T=35.0, 37.0 and
39.0◦C; and in case B at T=30.0, 33.0, 37.5, 40.0 and 42.9◦C.
In the case C, stationary states established at four different spe-
Fig. 3. Influence of (a) temperature and (b) specific flow rate on the analytical
signal. Conditions (a)–(A), (a)–(B) and (b) correspond to the cases A, B and C,
whereas in case C it is [MH]=0.022?mol.
cific flow rates j0=2.52, 2.80, 4.90 and 7.00×10−2min−1in
the vicinity of the higher bifurcation point were selected for
perturbation analysis.
In all cases, we found that the distance from the bifurca-
tion point decreases the sensitivity to morphine (Fig. 3). Hence,
conditions with highest sensitivity: T=39.0◦C (condition A),
T=42.9◦C (condition B), and j0=2.80×10−2min−1(condi-
tion C) were selected as optimal.
volume of analyte. For this purpose, the response of the matrix
that under the current set-up perturbations with volumes equal
to or larger than 500?L are not reliable because the dynamic
pattern changes additionally due to dilution. In the considered
cases, we found that there is some influence of the sample vol-
ume on the analytical signal (Fig. 4). Although, the analytical
signal increases with an increase of the injected volume, the
relaxation rate (defined as the time necessary for the matrix sys-
tem to revert to the initial stationary state) [25] is longer which
can be the problem in the kinetic determinations. Therefore,
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N.D. Peji´ c et al. / Analytica Chimica Acta 582 (2007) 367–374
Fig. 4. Graphic showing the ratio between the analytical signal and relaxation
time obtained as a function of the injected volume in experimental procedure B;
injection volume of 50?L was chosen for analytical purposes
because under these conditions the matrix system exhibited the
greatest ratio between intensity of signal and relaxation time
(Fig. 4).
The influence of a selected dynamic state on the sensitiv-
ity of the matrix system after perturbations is illustrated in
Fig. 5. Fig. 5(a) shows typical dynamic profiles for the pro-
posed matrix system obtained before and after perturbation of
system by morphine under the above-described experimental
conditions. Matrix response behavior is investigated by inject-
ing MH into the reaction mixture, when BL reaction is operated
under conditions where stable non-equilibrium stationary states
endured. Thus, before perturbation, the system is in a stable
stationary state and the corresponding potential denotes as Es
is constant. Injection of morphine causes an abrupt rise of the
potential to the value denoted Ep, which is the maximal value of
ent from the potential of the initial non-equilibrium stationary
3.2. Analytical procedure
Under the selected experimental conditions described above,
the response to the perturbations was measured by employ-
ing the change in potential as the measured parameter. It was
found that the maximal potential displacement, ?Em=Ep−Es,
is proportional to the intensity of the perturbation. A plot of the
?Emagainst the logarithm of injected morphine concentrations
provided a calibration graph that was fitted by the least square
The proposed method was validated according to the Inter-
national Conference on Harmonization guidelines [http://www.
tal noise level, whereas the limit of quantification was assessed
at a minimum signal-to-noise ratio of 10 [36]. LOD and LOQ
were experimentally verified by eight injections of morphine at
the LOD and LOQ amounts which all give acceptable precision
by the relative standard deviation (R.S.D.∗= (t × R.S.D.)/√n
with a theoretical t-value at 95% confidence limit for seven
degrees of freedom) and it was checked on eight samples con-
taining two different analyte concentrations (low and high)
within the calibration curve. Sample throughput (samplesh−1)
Fig. 5. Typical potentiometric responses of the BL matrix (experimental conditions A, B and C), obtained after its perturbing with morphine (a), together with
the numerically simulated time evolutions of the iodide concentration (b) under same conditions. The intensity of perturbations in A and B are (from left to right):
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Table 1
Features of the calibration plots and analytical figures of merit for the determination of morphine
Linear range
Regression equation,bY=A+Bc×X
LODd(?mol) LOQe(?mol)R.S.D.f(%)STg(samplesh−1)
aTotal amount of morphine in the 50?L aliquots of standard samples.
bY, maximal potential shift (mV); X, dynamic analyte concentration (?mol).
cInstrumental sensitivity (mVdecade−1).
dLimit of detection established at a signal-to-noise ratio of 3.
eLimit of quantification established at a signal-to-noise ratio of 10.
fFrom eight determinations of 0.005, 0.02, 0.09 and 0.2?mol of morphine.
gSample throughput is defined as a time needed for the system recovery after each perturbation.
hCorrelation coefficient (n=10).
stationary state after each perturbation.
As can be seen from Table 1, the calibration curves exhibits
excellent linear behavior over the concentrations range of about
one (experimental conditions A and C) and two orders (exper-
imental condition B) of magnitude with both, detection limit
ranged from 0.001 to 0.03?mol and instrumental sensitivity
from 22.1 to 28.5mVdecade−1. The obtained average R.S.D.
is 1.6%, which provides good repeatability for pharmaceutical
analysis. In summary, all experimental procedures perform well
in determination of morphine; however, for experimental proce-
dure B, the method is characterized by wider dynamic range, a
lower detection limit as well as the best sample throughput.
3.3. Selectivity
The extreme sensitivity of the reaction matrix to pertur-
bations, which is a positive trait for quantitative analysis, is
a negative feature when it comes to interfering species that
might be present in complex samples. Therefore, we investi-
gated the effect of some potential interferents from different
species such as some structurally related compounds to mor-
phine (monoacetylmorphine, codeine, acetylcodeine, thebaine,
matrix system was perturbed with solutions containing the fixed
amount of MH (0.022?mol) and studied external species with
foreign species and ions on the analytical signal was less than
on the determination of MH. The examined species were found
to interfere above the limit concentration ratio given in Table 2
in the form [interferent species]/[MH].
oscillatory matrix themselves may, also, influence the determi-
nation of morphine. Therefore, their effects were investigated,
some ions, such as I−, Br−and Cl−that were found to interfere
above MH interferent ratio 1:1 (they decrease analytical signal
probably due to a ring-substituted reaction with MH [37], but
they also interact with the matrix system [21]). Moreover, both
Ca2+ion and citric acid have strong adverse effect on morphine
determination, indicating that the proposed method is probably
less convenient for the analysis of biological material.
3.4. Sample analysis
The validity and practicability of the developed method for
the analysis of pharmaceutical preparation was exemplified by
assaying morphine injection, (packaged in 1mL ampules) that
was manufactured by Alkaloid, Skopje, FYR Macedonia. To
determine the morphine from this pharmaceutical preparation
(labeled to contain 20mgmL−1morphine hydrochloride), a
mercial sample in a 10mL volumetric flask and made up to the
volume with ethanol. Perturbations of matrix system were per-
formed with 50?L aliquot of the solution.
the seven replicate measurements of two independent solutions
of the same pharmaceutical, the average content of MH was
In order to test the accuracy of the procedure, additional
recovery experiments were carried out with the examined sam-
ple. The standard addition method is performed by accurate
Table 2
Tolerance to external species and ions in the determination of morphinea
Species and ions added Tolerable (interferent species
(/(MH( ratio
Fe3+, Na+
IO3−, cocaine
Starch, glucose, sucrose, carbamid
Heroine, caffeine
Codeine, acetylcodeine
Ascorbate acid
Acetylsalycilic acid, paracetamol
I−, Br−, Cl−
Citric acid
aMorphine concentration was equal to 0.022?mol.
bMaximum ratio tested.
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addition of 0.025?mol of MH in the dilute sample. The aver-
age recovery was 102.3% indicating that the method provided
accurate results. Also, the found result agrees with the reported
one by the producer (average R.S.D. is 1.1%). Hence, it is a
useful method for quantitative analysis of MH in pharmaceuti-
3.5. The interaction of morphine with BL matrix
Although it is not required for practical analytical applica-
tions to know the reaction mechanism between the analyte and
the matrix, we consider that it is relevant to address this issue
analyte and the matrix reaction is well understood, one can uti-
lize mathematical modeling as guide in a systematic search for
conditions where greater sensitivity and lower detection limits
can be achieved with the proposed method.
The BL reaction mechanism is rather well understood and
models with considerable predictive value have been pro-
posed and thoroughly tested [10,15]. To model the interactions
between morphine and the BL matrix, we selected to build on
the model consisting of eight reactions (Table 3) [15].
morphine reacted with the reactants of the BL matrix, which
were present in large excess. With this aim, we tested morphine
interactions with individual reactants and with binary mixtures
of reactants: H2SO4+KIO3, H2SO4+H2O2and KIO3+H2O2
in the CSTR. A potentiometrically recordable response to
morphine injections was observed only in the mixture of
that morphine does not react directly with any of the reactants,
even though they are present in large excess, but rather that the
mechanism of morphine interaction with the BL matrix is medi-
ated through the intermediates formed in the matrix reaction.
Thus, morphine interaction with the BL reaction mixture con-
taining highly reactive intermediates is certainly very complex,
one underlying phenol iodination in acidic aqueous solutions.
According to this mechanism, based on the assumption that the
attack of the iodinating agent upon the substrate is the rate-
limiting step, the kinetics of phenol iodination can be described
ide ion with hypoiodous acid [39]. Having this in mind, as well
as the known reactions between different organic compounds
and Briggs–Rauscher oscillatory reaction system having same
iodine species [40,41], we suggest, as the first approximation,
that morphine iodination, through interactions with hypoiodous
acid, is a crucial step through which the ratio between [HIO]ss
and [I−]ss, established in the stationary state before perturba-
tions is altered. Hence, we extended the model mechanism with
one new reaction:
where MH denotes morphine.
Validity of the proposed augmentation of the model is tested
in numerical simulations. The initial conditions are taken to be
the equal to the ones given in experimental procedures A, B
and C. To mimic the CSTR, the set of chemical reactions was
expanded by first order reactions to take care of the flows. In the
simulations, concentrations of all feed species ([H2O2], [IO3−]
and [H+]) as well as all intermediates were treated as dynami-
tration of sulfuric acid, though it is well known that H2SO4and
HIO3are not totally dissociated and that their concentrations
in the reaction mixture are not equal to the mixed inflow con-
centrations [42]. Rate constants for reactions I–VIII were taken
from the literature [11,15]. The rate constant for reaction (IX)
is estimated in such a way that the rate of this reaction is com-
parable with the rates of other reactions involving hypoiodous
acid at corresponding temperature (Table 3). A perturbation in
concentration of morphine in the course of integration of the
kinetic equations.
tion are shown in Fig. 5(b). The quantitative measure that char-
acterizes the effect of different MH perturbation strengths on
stable stationary state in BL matrix is the maximum potential
shift that corresponded to the change of logarithm iodide con-
centration caused by injection of morphine in BL matrix. A plot
of the ?E against the logarithm of injected morphine concen-
trations is linear. For the experimental conditions A, B and C,
the linear range, the slopes of obtained regression equation and
regression coefficient are all summarized in Table 4.
In summary, there is an excellent qualitative and quantita-
tive agreement between experimental and simulated results: the
form of the signal profile and the relaxation times are virtu-
Table 3
Mechanism of the model of the BL reaction
ReactionKinetic modelRate constants
k1=3.18×105M−3min−1and k−1=7.91×107M−1min−1
k3=5×103min−1and k−3=3.15×108M−1min−1
k4=3×1011M−1min−1and k−4=4.5Mmin−1
k5= k?
k8= k?
5+ k??
5[H+],k5= 1.2 × 104M−1min−1andk??
5= 3 × 104M−2min−1
8+ k??
8[H+],k8= 9.5 × 10−4M−1min−1andk??
8= 3.92 × 10−2M−2min−1
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N.D. Peji´ c et al. / Analytica Chimica Acta 582 (2007) 367–374
Table 4
The rate constants for morphine iodination and analytical figures of merit for determination of morphine obtained from numerical simulations
Experimental condition
k for iodination (IX) (M−2min−1) Linear range (?mol) Regression coefficientSlope (mV)
ally identical, and the linearity ranges are very well comparable
with experimentally determined ones. It is important to under-
line that agreement between numerical and experimental results
is obtained for all three conditions tested indicating that the pro-
posed model mechanism, though extremely simplified, reflects
well the dynamics of morphine interaction with the BL reac-
tion and can be used as a very good starting point for further
optimization of the method.
4. Conclusion
Our results demonstrate suitability of the use of the
Bray–Liebhafsky oscillatory reaction being in the stable non-
equilibrium stationary state in the vicinity of the bifur-
cation point, for morphine determination in the range of
0.004–0.18?mol in 50?L injected volume. The described
method offers high sample throughput (45samplesh−1), preci-
sion (R.S.D.=1.6%) as well as limit of detection (0.001?mol)
which all provide determination of morphine in the analyzed
provide a useful tool for morphine determination. In addition,
PPOSSS procedure is a good method for the accuracy morphine
determination (RCV=102.3%) in the pharmaceutical dosage
The described method has important advantages over any
method based on perturbations of the oscillatory reaction being
in the selected oscillatory phase point. Besides the mentioned
full analysis is shortened considerably.
The present investigations are partially supported by The
Ministry of Sciences and Environmental Protection of Serbia,
under the Project 142025.
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Map – Official National Park Service map of the central tourist area in Washington, D.C. Easy to use while outdoors, the map features large font sizes, walkways that are easily distinguishable from roads, and three zoom levels. By tapping the "Locate me" icon you will always know where you are.
Park Lens – Find out what is around you with augmented reality. Just hold up your device and look through the camera. Labels will appear identifying all sites on the National Mall.
Walking directions – Get from one place to another by following a line on the map or a list of directions. Estimated walking times are given.
Sites – Learn more about points of interest with lively text, professional photographs, and engaging podcasts under the "Album" button. The "Info" button includes the site's location, hours of operation, nearest Metro station, and other essential information.
Tours – Follow a recommended tour depending on how much time you have or your special interest—from memorials to presidents to military monuments to destinations off the beaten path. You can even create personal tours with the "My Tour" feature—just tap the "+" at the bottom right of a site page. The app maps the route for you.
Events and News – Get up-to-date information from the National Park Service about what is happening at the National Mall and Memorial Parks.
Postcard – Send a digital postcard to friends and family from the National Mall with the tap of a button.
Park Partner – The Trust for the National Mall strives to make the National Mall the best park in the world. Learn more about the essential assistance this organization provides.
Small size – Weighing in at 13.7MB, the app will download relatively quickly via a 3G cellular connection or the free Wi-Fi available on the east end the National Mall.
What's New
America's National Parks
Passport: Your National Parks
A map feature provides easy access to the location of more than 1,000 Passport to Your National Park cancellation locations. Park listings identify the year and stamp type when featured on the annual Passport commemorative stamp sticker set.
This digital Passport Companion allows you to explore every unit of the National Park Service, mark parks you would like to visit and those you have visited. You can search parks by name, state or "nearby" using GPS technology. There is a digital scrapbook for each park that allows you to log a journal entry, record the date of your visit, and import photos with descriptions. You can find park addresses, phone numbers, National Park Service websites, plus entrance fee and junior ranger program information.
- Includes valuable information on every unit of the National Park Service
- Search for parks alphabetically, by state or Passport region
- Find Passport cancellation stations by map or list
- Create journal entries for your park visit
- Add photos, with descriptions, to visited sites
- Mark parks you would like to visit or have already visited
- Find nearby parks using GPS map feature
- Follow links to National Park Service website for directions, hours, events and more
- One-touch access to eParks.com, the Official Online Store of America's National Parks
Chimani National Parks
The key features of the app include the following:
★ Simple Interface - Interaction with the app using Chimani's unique interface based on universal national park symbols.
★ Passport Stamps - Record the years you've visit a National Park Service unit and create a "Someday/Maybe" list.
★ Someday/Maybe - Create a "Someday/Maybe" list of units and parks which you plan to visit!
★ News - Access daily national park news provided by National Park Traveler News website (in-app purchase required).
★ Search - Use the lighten-fast search engine to find anyone of the 400 units within the app.
★ Details - Learn about the rich history in each one of the National Park Service units (content provided by Wikipedia).
★ Location - View the location of each unit on interactive maps.
*** This app requires an inital Internet connection to download photos (either Wifi or cellular). ****
Chimani is the leading developer of mobile app to help you explore our National Parks. Learn more at: www.chimani.com
National Parks - Volume 1
These pictures portray the best that the U.S. Park System has to offer. An introductory description of each park beckons you to make the virtual journey into Grand Canyon, Yosemite and more of nature's best places on the planet.
Smithsonian VisitorGuide/Tours
We've designed a special FREE tour of the presidential and first lady highlights from the Smithsonian collections. You'll get easy turn-by-turn directions to five of the Smithsonian museums from the Natural History, American History and American Indian museums on the National Mall and from the National Portrait Gallery and the American Art Museum in the Penn Quarter District.
Our latest new postcard, lets you snap a photo of friends and family wearing George Washington's uniform; and share it instantly on Facebook and Twitter.
This limited edition FREE tour is your entry ticket to our full Smithsonian Tours App. For just 99 cents, you can upgrade to a whole suite of our best tours of the Smithsonian and select from a host of digital postcards to wow your friends. Send home a picture of your mom wearing the Hope Diamond and the Ruby Slippers from Wizard of Oz, or hangout with an orangutan or swim with a giant squid. All with your 99 cents upgrade.
For just 99 cents, get the most out of your trip to Washington, D.C. and the National Mall with custom-built tours, based on your available time and passions. From the editors of Smithsonian magazine, Smithsonian Tours is packed with handy navigational tools, maps, museum floor plans, a calendar of events, dining and shopping, including 'Greatest Hits' for each Smithsonian museum.
What can you do with the Smithsonian Tours app?
- Based on your interests, size of your group and available time, we offer "Greatest Hits" tours of the Smithsonian's Washington, D.C. museums. Art Lover, Nature Lover and History Buff, or find tours to take With Dad, With Mom or With the Kids.
- Check out our list of Must-See Exhibitions and get updates on daily events.
- Get turn-by-turn walking directions on the map of the National Mall, locate artifacts inside the museums and find the nearest Metro stops.
- Get hot news tips from the Smithsonian and the Around the Mall blog on Smithsonian.com.
- Navigate with maps, directions, augmented reality and a handy Friend Finder to locate your lost pals.
- Remember and share your time at the Smithsonian by sending a custom digital postcard. Put yourself inside the Apollo 11 Command Module, wear the Hope Diamond, step out in the Ruby Slippers or hang out with the Orangutan at the Zoo. Pick from our other fun selections and send them to your friends.
- Find out where to eat and shop with descriptions of Smithsonian restaurants and stores.
- The app has selections from all of these museums: the Air and Space Museum, the American History Museum, the Natural History Museum, the Smithsonian Castle, the Udvar-Hazy Center, the African Art Museum, the American Indian Museum, the Anacostia Community Museum, the Freer Gallery, the Sackler Gallery, the Hirshhorn Museum, the National Portrait Gallery, the Postal Museum, the Smithsonian American Art Museum and its Renwick Gallery, and the National Zoo.
Museums In Washington DC
Museums In Washington DC isnt a digital yellow pages like most museum apps. You get useful info like:
-choose by category
-choose by selecting museum from a map
-1 touch navigation to address
-directly email & phone museum
-hours of operation & cost
-easily link to collections,events,etc
-rental & intern availability
-Museum Community
Museums In Washington D.C. includes a special link listing all Smithsonian museums regardless of category (although they are included with their default category. For example, the Air & Space Museum is listed in both the Smithsonian and Science links). This is available from the list links or from the maps.
Follow on Twitter @AndroidsFuture
NPS Yosemite
- 50+ Sites including natural and cultural landmarks and destinations
- Locations, hours and other details for Services within Yosemite including Camping, Lodging, Shuttles, Recreation and Tours, and more
- Up-to-date listing of daily Programs including free and paid programs offered by the National Park Service and park partners such as Yosemite Conservancy, The Ansel Adams Gallery, and DNC Parks & Resorts at Yosemite.
- Interactive Map of Sites including popular Yosemite Valley destinations
- 20+ suggested Day Hikes throughout Yosemite National Park
- Browse @YosemiteNPS twitter feed and blogs
- Find answers to the most common questions about visiting Yosemite
- Learn more about Yosemite Conservancy and other park partners
Cellular service is limited in many parts of Yosemite National Park. Some features, content, and links require data connection. This app is not intended for use as a GPS-based navigation aid.
Smithsonian's National Zoo
Our app provides detailed maps, parking information, animal viewing, special events, and tour highlights. Information on each animal species can be viewed using search functions, by name, category, and location. The National Zoo's conservation programs are also highlighted. Just for fun, the app incorporates a Zooify Yourself feature to create your own animal features using any picture along with Animal Voices. The app provides a "connection" to all our social media initiatives along with the ability to support the National Zoo.
Arches National Park
• Favorite destinations
• Things to see and do in the park
• Stunning photos
• A park map that includes all of the roads and hiking trails in the park.
• Ranger-led activities
• The Junior Ranger program
• Locations of services within the park such as the visitor center, restrooms and picnic areas.
• Permit information, safety guidelines, and tips – including how to maximize your visit, photography tips, campground information and much more!
Canyonlands Natural History Association has been the official non-profit partner of Arches National Park since 1967.
National Parks Depot
Parks Seeker
With Parks Seeker, you can:
• Easily track your progress of parks visited and those still waiting to be explored
• View detailed information about all 59 national parks
• View an interactive map displaying parks and your check-ins
• Check in to parks based on your current location, or create check-ins for past visits
• Add a photo to each check-in
• Share your visits through Facebook, e-mail and text
• Create a wish list of the parks you'd like to visit next
• Locate the park closest to you based on your current GPS location
Parks Seeker includes all 59 of the United States' active National Parks:
Acadia · American Samoa · Arches · Badlands · Big Bend · Biscayne · Black Canyon of The Gunnison · Bryce Canyon · Canyonlands · Capitol Reef · Carlsbad Caverns · Channel Islands · Congaree · Crater Lake · Cuyahoga Valley · Death Valley · Denali · Dry Tortugas · Everglades · Gates of the Arctic · Glacier · Glacier Bay · Grand Canyon · Grand Teton · Great Basin · Great Sand Dunes · Great Smokey Mountains · Guadalupe Mountains · Haleakalā · Hawai'i Volcanoes · Hot Springs · Isle Royale · Joshua Tree · Katmai · Kenai Fjords · Kings Canyon · Kobuk Valley · Lake Clark · Lassen Volcanic · Mammoth Cave · Mesa Verde · Mount Rainier · North Cascades · Olympic · Petrified Forest · Pinnacles · Redwood · Rocky Mountain · Saguaro · Sequoia · Shenandoah · Theodore Roosevelt · Virgin Islands · Voyageurs · Wind Cave · Wrangell–St. Elias · Yellowstone · Yosemite · Zion
If you like Parks Seeker, you may also enjoy Summit Seeker—the app that tracks your progress conquering the highest point in all 50 states!
Parks Seeker can use your GPS location to find the closest park to you, but the app does not require data or cellular service to use most features!
National Mall Audio Tour
While many of these memorials, such as the majestic Lincoln and Jefferson Memorials, are famous, this tour also features lesser known sites that are no less beautiful or significant, such as the obscure Memorial to the Signers of the Declaration of Independence. The tour is designed so you can start anywhere you like and go for as long as you like, whenever you want. The National Mall is open 24 hours a day and is beautiful and fascinating anytime of day or night. If you visit all 27 stops on the tour, it could take several hours to complete, but you can always go back ~ the tour is yours to keep and can be used again and again.
On this tour you will learn the history of a great nation and its people, the controversies surrounding their accomplishments, and the stories by which we remember them. Highlights include the Washington Monument, Jefferson Memorial, Lincoln Memorial, Vietnam War Veteran's Memorial Wall, Vietnam War Veteran's Memorial Bronze Statue, Korean War Memorial, National World War II Memorial, The Vietnam Women's Memorial, WWI Memorial, Martin Luther King Jr. Memorial, Franklin D. Roosevelt Memorial, the George Mason Memorial, John Paul Jones Memorial, Memorial to the Signers of the Declaration of Independence, and the Memorial to Franklin Delano Roosevelt.
Bryce Canyon National Park
Bryce Canyon National Park is your essential pocket guide to this visually stunning travel destination. Our app gives you these incredible features:
- A built-in offline map that provides detailed park location data without an Internet connection
- Trail information and GPS-based trail maps for 17 popular trails
- Over 50 photographs covering each stop on Scenic Drive
- Handy information about camping near the park
- A FREE, optional US Geological Survey topo map
Scenic Drive GPS Guide
This app provides a hands free, voice narrated guide to help you enjoy the incredible vistas and unusual hoodoos of the 18 mile Bryce Canyon Scenic Drive. The GPS guide contains information for all stops on the Scenic Drive. No need to look down at your guide book or flyer -- just tap the Start GPS Guide button, start driving, and it will notify you as you approach each stop! A brief recommendation about each stop is narrated to you. Then, when you arrive at the stop, a photo pops up, and a complete description is narrated to you.
Nothing could be easier AND no cell phone connection is required! That's right, all information, including an offline map, is included in the downloaded app. Once installed, just be sure to enable your GPS satellite option, and your hands-free guide to Bryce Canyon Scenic Drive will do the rest.
This is the same technology used in our popular Maui Road to Hana app, which has been described as:
"(an) indispensable guide...The voice guide made it feel like we had a tour guide in the car with us"
Offline Map
Our app includes a complete offline map, for Internet and cell-phone connection free access to detailed park information. This map is built into the download -- as soon as the app is installed, the map is ready. No further Internet access is needed to use the app!
Add On US Geological Survey Topo Map for Offline Use
The US Geological Survey topographical map -- commonly known as the "topo map" -- is the gold standard in mapping for remote locations. And now you can have access to this map, specifically for the Bryce Canyon Scenic GPS Guide, at any time -- and completely offline! A one-time download is all it takes*. The maps offer scales from about 1:15,000 down to 1:4,000, plus an additional zoom level to make reading the small type on these maps easier.
* Topo map download size is about 101 Megabytes
For an explanation of the Android permissions this app uses, please visit:
USA National Parks
2)User can get the information about park like animals,points of attraction,nearest city and many more.
3)Easy search is also available in the App.
4)With the help of map user will know in which state the park is situated.
Yosemite National Park Gallery
Indian National Parks
What makes this app unique is its off-line availability. The crisp information which it covers is indicative of what you can achieve on a typical outing to these National Parks. You would find the quick information on the following in this app:
a) State/Union Territory, where it is located
b) Year of Establishment
c) Total Area
d) Known For - Avian fauna, Mammals, Reptiles and Amphibians you can date with :)
You may find this app useful in planning your trip. I hope you will enjoy your tryst with Nature in exploring some of the most exquisite scenic and historic treasures in India.
FOLLOW US and stay in touch to get all the latest information about "Indian National Parks" and other exciting Apps and future updates:
More from developer
NPS Independence
Map – Official National Park Service map of the historic area of Philadelphia. The map is easy to use while outdoors, features large font sizes, illustrated walkways that are easily distinguishable from roads, and multiple zoom levels. By tapping the "Locate me" icon you will always know where you are.
Sites – Tap the "Sites" button to learn more about points of interest with lively text, professional photographs, and engaging audio. The Visiting section includes the hours of operation and other essential information.
Tours – Discover the Road to Revolution or follow in Benjamin Franklin's footsteps on guided audio tours throughout Independence National Historical Park.
Special Events and Programs – Get up-to-date information from the National Park Service about what is happening at the Independence National Historical Park.
Postcard – With the tap of a button, share a digital postcard with friends and family from Independence National Historical Park.
Small size – Weighing in at around 26MB, the app will download relatively quickly via a 4G cellular connection or the free Wi-Fi available in the Independence Visitor Center.
NPS Boston
On your next visit to Boston, use it to explore many of the most important cultural and historical sites in the United States— Old South Meeting House, Old State House, Faneuil Hall, Old North Church, Paul Revere House, Bunker Hill Monument, Bunker Hill Museum, Dorchester Heights, and the Charlestown Navy Yard including USS Constitution, the USS Constitution Museum, and USS Cassin Young. Every site along Boston's Freedom Trail® is featured.
Boston African American National Historic Site is comprised of the largest area of pre-Civil War black owned structures in the U.S. Learn about the homes, businesses, schools, and churches of a thriving black community that, in the face of great opposition, fought the forces of slavery and inequality.
- Check out historic sites and events with text, audio, images, and video.
- Choose thematic tours, staff picks, or build your own tour.
- Explore the official National Park Service map of Boston that includes large font sizes, easy to distinguish walkways, and dimensional buildings.
- By tapping the "Locate me" icon you will always know where you are.
- Walking directions – Get from one place to another by following a line on the map or a list of directions. Estimated walking times are given.
- Discover alternative modes of transportation.
- Find other national parks and historic sites in the region and across the country.
NPS Yellowstone Geysers
Webcam - If you can't make it to the park, watch a live eruption of Old Faithful and other geysers in the Upper Geyser basin though an integrated webcam.
Social Media Feed - Learn what is happening in Yellowstone by browsing content from the park's Twitter, YouTube, and Flickr sites.
Photo Gallery - Each eruption is different, so enjoy a collection of geyser photos.
FAQ - Want to know more about geysers? We have answers to some of the most frequently asked questions.
NPS Chesapeake Explorer
The Chesapeake Explorer app helps you discover the places where you can experience the Bay region's beauty, history, and heritage firsthand. Find and visit places by activity, trail name, or type of site. Take a suggested tour, build your own tour, tag favorites, share photos of your visit or save places for visiting later. The app includes over 400 sites across six states.
Plan Your Visit – plan your visit to one or several of more than 400 parks and historic sites in the Chesapeake –find locations, hours of operation, fees, and other helpful information. Learn the history of some these natural areas and historic places.
Maps – enable geo-location to find sites nearby, zoom in and out, and finger-scroll to better view sites. Generate driving directions on demand to any site in the app.
Search by Nearby -- find places near your physical location or draw your own map extent to find fun and exciting places to visit.
Search by National Park or National Trail – locate national parks and trails nearby, or access a comprehensive list. Plan your visit to one or more places on the Star-Spangled Banner National Historic Trail, Captain John Smith Chesapeake National Historic Trail, Potomac Heritage National Scenic Trail, or Chesapeake Bay Gateways and Watertrails Network.
Search by Activity -- find hiking, biking, boating, fishing, camping, and birdwatching opportunities nearby.
Search by Site Type – locate nearby parks, preserves, trails, or historic sites and museums, or view a comprehensive list to help you plan your visit.
Suggested Tours – follow suggested history, driving, biking or walking tours. Tours provide turn-by-turn directions and approximate travel times.
My Tour -- create personal tours -- just tap the "+" at the bottom right of a site page. The app maps and saves the route for viewing later. Edit tours anytime and get driving directions.
My Favorites – tag your favorites to revisit later.
Add to Places Visited – tag sites visited and keep track of your explorations throughout the Chesapeake region.
Share the Adventure – share your visit on Facebook or Twitter, or email friends and family.
Send a Postcard – snap a photo to remember your visit, or send a digital postcard to friends and family with the tap of a button.


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Inside a 'Gold Rush'
For 'The Dirt,' a run-up to the anticipated 'Gold Rush: South America,' a producer offers a candid look behind the scenes.
Surf Towns, Reborn Cities, and Mountain Meccas Where Life is Good
Plus: Inside Climbing's Toughest Triumph
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Mega event with Stone Cold Steve Austin, John Cena, Hulk Hogan, Sting as 'WWE 2K15' roster revealed during SummerSlam Weekend
LOS ANGELES - A sports entertainment dream team, past and present, participated in the big reveal of the "WWE 2K15" roster at Club Nokia.
John Cena, Hulk Hogan, Cesaro, Sheamus, Roman Reigns and Sting took the stage for the event, which aired live on IGN. WWE Hall of Famer Stone Cold Steve Austin and WWE broadcaster Renee Young served as moderators, asking and fielding questions for the special SummerSlam Confidential panel.
By the way, "Stone Cold" is the toughest S.O.B. to ever wear reading glasses.
The names announced for this new WWE video game (available Oct. 28 in the United States and Oct. 31 internationally) included a mix of familiar faces and others appearing for the first time, like Naomi, Bray Wyatt & the Wyatt Family and Sting.
Although he appeared at the San Diego Comic-Con, the WCW legend remarked that the 'WWE 2K15' event was his WWE debut. He made no bones about wanting to face The Undertaker at some point, maybe at a WrestleMania. When asked by a fan who he wanted his last opponent to be, he jokingly responded, 'RoboCop,' a nod to his stint working with the film character in WCW.
Austin and Hogan threw some fun jabs at one another as who really is the best. The Hulkster also gave his SummerSlam prediction for the WWE World championship match, choosing Cena over Brock Lesnar.
In between the roster reveal, the panelists reflected on their respective careers, rivalries and how they started in the business. Cesaro and Sheamus went back-and-forth about who was the better European superstar.
Of course, the $9.99 jokes promoting WWE Network were mixed in.
Roman Reigns showed a lot of personality, and his love for the industry can be traced to a picture of him as child being held by Hogan. Reigns met many wrestlers as he grew up in the business. His father, Sika, is one-half of the WWE Hall of Fame tag team the Wild Samoans.
For his efforts in WWE (so far), Reigns, the former enforcer of The Shield, earned a pat on the back from Austin.
Dean Ambrose, another former Shield member, got one too, as Austin referrred to him as his drinking buddy.
The VIP ticket holders who attended posed for a photo with Reigns after the panel concluded.
Other SummerSlam Confidential panels were conducted throughout the weekend, featuring Triple H, Shawn Michaels, Hogan and Austin. Artist Rob Schamberger was a special guest, painting a portrait of Stone Cold. Schamberger also set up a table during the events.• Visit http://wwe.2k.com for more information and updates regarding the video game.
Follow @WWEGames on Twitter.• John Cena defends the WWE World championship against Brock Lesnar (with Paul Heyman) 8 p.m. EST Sunday, Aug. 17 on pay-per-view and WWE Network from the Staples Center in Los Angeles. For everything surrounding the event, visit www.SummerSlam.com.
• Look for upcoming features on Hogan, Austin, Sting and others.
• Follow me on Twitter @smFISHMAN.
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