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Clearwater High School Indians
Clearwater opened in 1960. The school is located at 1201 E. Ross in Clearwater. The 4A Indians play in Division IV of the Ark Valley-Chisholm Trail League. Clearwater has won six state championships: boys basketball (1949), boys track (1944, 2005), wrestling (2003), girls cross country (1987), volleyball (1994).
2014-15 basketball preview: Clearwater
December – 5, Kingman; 8-13, at Cheney tournament (B&G); 16, Circle; 19, at Collegiate. Full Story →
VarsityKansas Big Show (Nov. 11)
Clearwater football coach Dirk Ankerholz joined The Wichita Eagle's Joanna Chadwick in this week's Big Show. Full Story →
Clearwater football improves at perfect time
A lack of experience combined with a brutal first five games added up to a big zero in the wins column for Clearwater's football team. Full Story →
Andale volleyball uses hitting depth to win two matches
If Andale setters wanted to, they could set the volleyball to senior Rachel Friedrichs every possession and find success. She's a dominating presence at the net and can hit middle or pop outside. Full Story →
Football 2014: Clearwater Indians
Clearwater has two quarterbacks, but only one actually plays quarterback. Full Story →
The 2014 Wichita Eagle/VarsityKansas.com high school football video and photo shoot
Highlights (including pictures) Full Story →
4A-II softball: Pratt beats Clearwater in championship game
Pratt rolled over Clearwater 12-2 to win the Class 4A-Division II softball title on Friday. Full Story →
4A-II softball: Pratt, Clearwater advance to semifinals
PRATT – The Clearwater Indians and Pratt Greenbacks won their quarterfinal games in the Class 4A-Division II softball tournament on Thursday. Full Story →
Softball notes: Clearwater ramps up for postseason
One of Clearwater softball coach Chuck Schrader's primary concerns for the 2014 season came true in the Indians' third doubleheader, a sweep at the hands of Rose Hill. Full Story →
Rose Hill looks sharp in sweep
First-year softball coach Kim Waltman understands she has a team full of perfectionists at Rose Hill, whether they are on the field or in the classroom. Full Story →
Basketball roundup: Collegiate boys defeat Mulvane
Cameron Christian hit a season-high 26 points to help Collegiate defeat visiting Mulvane 74-51 Thursday night. Full Story →
Roundup: Mulvane girls win own tournament title
KaSandra Melick and Aubree Burkhart scored 17 points each to lead Mulvane's girls basketball team to its own tournament title, beating Garden Plain 54-48 on Saturday. Full Story →


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Area drivers have to adjust to new interchange
The signs that adorn the new interchange, scheduled to open Wednesday, with other routing changes slated for the area in coming months.
Dot Paul/Staff
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To The Gallery
Order a print of this picture
Athens, GA • Athens Banner-Herald ©2014. All Rights Reserved.

subset: commoncrawl


text:
College Town Junior School Wake Up Club.
Daily from 8:00am-8:50am. £1.50 daily, no need to book.
Children must be signed in by an adult.
Like what you see? Leave a message on our "Guestbook" page
Click the notice board for news articles.
Latest school term dates Events
- Clubs finish this week.01Dec2014
Cubs finish this week. Please check with external fee paying clubs for further information.
- Lower School Christmas Performance10Dec2014
09:30 am - 11:00 am @ 9:30 am & 7:00pm
Pre-booked tickets only-details to follow.
- Upper School Christmas Performance11Dec2014
09:30 am - 11:00 am @ 9:30 am and 7:00pm
Pre-booked tickets only-details to follow.
Academic year 2014/15 -Please note that some of our Staff Training Inset days may differ from other Bracknell Forest Schools.


text:
This looks like her death certificate although the date of death is 9 August 1976:
She is the second one on the page, click on her name and you'll have the info. You may also view the original. Note that the informant is her mother Brenda but the last name is spelled "FORSTON" yet the infant is listed as "FORTSON", a typo or...? Name of father is not given on the death certificate. Hope this helps.
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text:
Flymo petrol hedge trimmer
Flymo petrol hedge trimmer was bought working but never used as the fuel pipe was burst. That's been replaced but no longer required.
Flymo petrol hedge trimmer was bought working but never used as the fuel pipe was burst. That's been replaced but no longer required.
Viking stihl vh540 rotavator vgood condition 22in cut and 30in cut with extentions please tx and I'll get back to you
JCB Petrol Strimmer for sale. Used condition. Looking for around £50 call 07925345259
Proline 1800w garden chipper\shredder. Will take branches upto 37mm. Good working order.
I have a fully working serviced push petrol lawnmower. In good working order and ready for next season with grass box. Its a very good Briggs and Stratton 35 engine which has been serviced and ready to go. May deliver localy for a small cha
Briggs & Stratton 3.75HP 4-stroke engine excellent condition £50 ono.
I have a Flymo garden vac/blower and 2 electric hand held cultivators for sale. Job lot of £40 or will sell separately at Garden Vac/Blower - £45 Hand held cultivators - £10 each
No longer needed as moving house. Only used a couple of times. Has full spool of strimmer cord. £25 on Amazon. Sell for £15
Metal blades. Used four times. No longer needed as moving. Comes with grass collection box. £64 on Amazon. Will sell for £25
This very powerful leaf blower (2200W) will get your garden looking amazing for winter in no time. Use this for two functions, blowing, collecting and munching.
Black & Decker Safe 'n' Tidy Cable Reel Heavy Duty 40m (130ft) Cable Reel - For use with outdoor power tools in longer gardens - Fitted with Plug (fused 13 amp) & Connector (2-pin) to fit ALL Black & Decker garden power tools. - heavy duty 2-core
Mountfield 35 Classic self propelled lawnmower. It was running well until this summer. FOR SPARES OR REPAIR.
NOW OPEN TO OFFERS HOUSE MOVE FORCING QUICK SALE Honda engine Flymo base Great condition Only been used about 30 cuts since new so engine excellent . Would benifit from a service but doesn't need one . Slight wear in the cable but doesn't affect
NOW OPEN TO OFFERS HOUSE MOVE FORCING QUICK SALE Honda engine Flymo base Great condition Only been used about 30 cuts since new so engine excellent . Would benifit from a service but doesn't need one . Slight wear in the cable but doesn't affect
Ex Bowling Green self propelled Ransomes 20" Auto-Certes with Kubota GS 160. 3.7hp engine, great heavy duty roller would suit medium to large lawn.
Flymo strimmer. Working! very Good condition. Open to to offers. I think i am being reasonable with the price.
Second Hand Ferrari 350 Rotovator. (Worth £1500 second hand when in good working order.) Needs some work, clutch cable broken, brakes need adjusting. Runs fine. Moving premises so reduced price. Quick sale required.
lawnmotor for sale only thing wrong is basket has to be hold on with a screw as little clip broke doesn't affect it atall tho great working order
Lawnmower Collect only. Please contact me on 07754492868 thank. No time wasters please. I live near bridge of cally blairgowrie.
Mcculloch petrol strimmer . Model no mt 260 gls. Brand new . Never out of the box. I am including a petrol mixer and bottle of two stroke oil. This model has the ability to accept other fitments. Detatchable strimmer part. Twin line. . Cost £126.99
Used Qualcast Hover Lawn Mower Model: GHM145A 230-240v 32cm cutting diameter Cutting height 12-32mm PLUS Qualcast Strimmer £60 ONO for both Sold as seen. Collection Carluke or I can deliver for extra charge. Other items fo
Ride on mower in good working condition,been dry stored since new,1 owner. 8HP BRIGGS Only used for five hours since service. Battery does not hold a charge so will need to be replaced at start of season. Starts with jump Comes with owners manua
I need a sthil saw...cash waiting for a good one!!
I need a Sthil saw...cash waiting for a good one!!
Honda FG 201 4 stroke rotovator. Choice of 2 - FG201's Fully serviced ready to go to work. Perfect size for your Veg plots or Flower Beds. No mixing oils & fuel. 4 Stroke. Dip the oil - Petrol in the tank - Off you go. To buy new £500 - Looki
Honda FG200 4 Stroke rotovator Fully serviced. Ready for work. Lovely machine - Nice size. To buy new £500 - Looking for £250
Excellent condition. Ideal for cleaning large areas - for removing & shredding leaves and cuttings. Can also be used for blowing snow, leaves etc. Fully serviced. Stihl ErgoStart easy start function. Stihl anti-vibration system. Complete with
Westwood G5 petrol rotovator,forward and reverse, had from new very powerfull 5 horse Briggs and Stratton engine,light work in an allotment, handles move from side to side very good condition £180 ovno
Qualcast Panther 30 push lawnmower with collection bucket. Seldom used and condition good.
Hi putting this on for a friend gd running and cutting £600 ono thanks for looking
Hi am putting this on for a friend it's a ransomes mag gs130 gd running and cutting easy to start if u want to no anything els just ask selling for £600 ono thanks for looking


text:
Ready For Summer by Heidi Smith
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text: Refined and elegant, the Prima Donna Belleville full brief panty is a perfect fit every time. Surround your curves in smooth, satiny microfiber and delicate scalloped edges. The floral and dot embroidery combines modern touches while still remaining timeless. The full rear coverage and high-waist conceals while the sheer tulle reveals. Providing full coverage with accents describes the Prima Donna Belleville collection in every way.


text:
B-King '08-'12
B-King '08-'12
MRA RacingScreen (style "RNB") universal windshield for naked sport bikes, cruisers, enduro and dual sport motorcyclesMRA RacingScreen for Naked Bikes are available in Clear, Smoke Gray tint, Gloss Black & Satin Black. 14.7" (373mm) tall x 17" (431mm) middle width x 12" (304mm) top width. Learn More$99.99
Oxford Maximiser 360T - multi-purpose 12-volt motorcycle, car, truck & marine battery chargerOxford's smart 3600mA charger with multiple charging rates which analyzes battery condition, will check polarity, and "float", or maintain a charge for battery longevity. Suitable for all 12 volt motorcycle, car, truck and leisure batteries. Learn More$74.99 $41.99
R&G Plug 'n Play Micro Indicators turn signals (Incandescent 10 watt)R&G Plug 'n Play Micro Indicator turn signals (pair). Includes 10 watt incandescent bulbs; replaces original 10 watt or 21 watt incandescent turn signals. Designed to fit the R&G line of "Tidy Tail" fender eliminators. Learn More$48.99
Kaoko Throttle Lock Cruise Control for Suzuki B-King, Bandit GSF1250(A/FA/SA), GSF1200, GSF650(A/S/N/SA), GSF600(S/N), TL1000(S/R), GSX-R1000, GSX-R750, GSX-R600, GSX650(F/FA), GSR750, GSR650, GSR600A, SV650, SV650SF, & Kawasaki KLR650A '86-'07Kaoko Cruise Controls are purpose-built for a variety of motorcycles over 600cc. They consist of a friction nut that is integral with a replacement handlebar-end weight. Learn More$144.99
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Scottoiler vSystem Vacuum Operated Chain Oiler for all Motorcycles with EVAP SystemsKeep the drive chain and sprockets on your motorcycle properly lubricated while you ride with the Scottoiler vSystem Vacuum Operated Chain Oiler. Learn More$129.95


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realmagick.com The shrine of knowledge.
John W Snow Career
A selection of articles related to john w snow career.
Original articles from our library related to the John W Snow Career. See Table of Contents for further available material (downloadable resources) on John W Snow Career.
- King James Bible: John, Chapter 1
- Chapter 1 1:1 In the beginning was the Word, and the Word was with God, and the Word was God. 1:2 The same was in the beginning with God. 1:3 All things were made by him; and without him was not any thing made that was made. 1:4 In him was life; and the life...
New Testament >> John
- King James Bible: John, Chapter 3
- Chapter 3 3:1 There was a man of the Pharisees, named Nicodemus, a ruler of the Jews: 3:2 The same came to Jesus by night, and said unto him, Rabbi, we know that thou art a teacher come from God: for no man can do these miracles that thou doest, except God be...
New Testament >> John
- King James Bible: John, Chapter 10
- Chapter 10 10:1 Verily, verily, I say unto you, He that entereth not by the door into the sheepfold, but climbeth up some other way, the same is a thief and a robber. 10:2 But he that entereth in by the door is the shepherd of the sheep. 10:3 To him the...
New Testament >> John
- King James Bible: John, Chapter 5
- Chapter 5 5:1 After this there was a feast of the Jews; and Jesus went up to Jerusalem. 5:2 Now there is at Jerusalem by the sheep market a pool, which is called in the Hebrew tongue Bethesda, having five porches. 5:3 In these lay a great multitude of...
New Testament >> John
- St. John's Wort: Correspondences
- Hypericum perforatum Poison Folk Names: Amber, Fuga daemonum , Scare-Devil, Goat Weed, Herba John, John's Wort, Klamath Weed, Sol Terrestis, Tipton Weed Gender: Masculine Planet: Sun Element: Fire Deity: Baldur Power: Protection, Health, Strength, Love...
Herbalism >> Herbs dictionary S
- The Twilight of the Celtic Gods
- The Milesians, according to myth, were the first Celts to settle in Ireland. This group was named after the eight sons of Mil (some texts say King Milesius); these Gaelic peoples, the myths report, came to Ireland from Spain. Ironically, the first phase of...
Saga of Times Past >> Legend and Prehistory
John W Snow Career is described in multiple online sources, as addition to our editors' articles, see section below for printable documents, John W Snow Career books and related discussion.
Suggested Pdf Resources
- John W. Slocum, Jr.
- John Slocum is the Chairperson of the Management and Organizations .. W. Cron and J.
- jschoen.cox.smu.edu
- John W. Severinghaus, M.D.
- Who influenced you the most to pick a career in medicine, a career in W. Andrew Kofke, M.D.
- www.auahq.org
- Shore of Virginia-up into Worcester County, Maryland, near Berlin and Snow Hill A: His father, my grandfather, owned a clothing store-John W. Morris and Sons .. That's how I got on the track squad and had a very successful career in track.
- 22.214.171.124
- Surv., 1903, pp. 271-287.
- www.nap.edu
- Oral Histories: Dr. John W. Gofman, M.D., Ph.D.
- This section, on Dr. John W. Gofman, M.
- ratical.org
Suggested Web Resources
- John W. Snow - Wikipedia, the free encyclopedia
- en.wikipedia.org
- John W. Snow Profile - Forbes.com
- Dr. Snow, 71, is President of JWS Associates, LLC, a consulting firm. He was the U.
- people.forbes.com
- John W. Snow Biography - children, school, young, born, house
- Several jobs at the U.S. Department of Transportation, including assistant secretary, John W.
- www.notablebiographies.com
- John W Snow Career | RM.com ®
- John W Snow Career articles, reference materials. Need more on John W Snow Career? We suggest these original texts: The Story of John W Snow Career roots.
- www.realmagick.com
- John W. Snow financial definition of John W. Snow. John W. Snow
- Definition of John W. Snow in the Financial Dictionary - by Free online English dictionary and He began his career at the Department of Transportation.
- financial-dictionary.thefreedictionary.com
Great care has been taken to prepare the information on this page. Elements of the content come from factual and lexical knowledge databases, realmagick.com library and third-party sources. We appreciate your suggestions and comments on further improvements of the site.
John W Snow Career Topics
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text:
Latte Polished Steel and Dark Walnut Floor Lamp
Switch: 3-way Shade attachment: Spider Overall Height : 31 Cord Length: 72-Inch Bulb Included Shade Width: 17 Shade Height: 12 Shade Material: Fabric
Switch: 3-way located on socket Shade attachment: Square spider Base Dimensions: 8-Inch W Overall Height : 26 Cord Length: 72-Inch Bulb Included Shade Width: 14 Shade Height: 9.5 Shade Color: Off-White Shade Material: Fabric
Suede Shade
Each Lexington lamp has a dark walnut wood body with satin steel accents and base. The alabaster frosted glass shade is anchored by a satin steel cap with matching finial. Two sockets each have ball-accented pull chain. 2 x 60 Watt. 22.5 inch Height, 8.5 inch Round base. Shade: 6 inch Height, 13.5 inch Diameter.


text:
A pimp's term for a blonde, blue-eyed white hoe.
"Lemme get that pepperwood jaunt"
by Carl E October 21, 2008
10 Words Trending Now
Alphabetical List
Type your email address below to get our free Urban Word of the Day every morning!
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text:
BASF Corporation
1 person found this helpful
"BASF Project Manager Review - Freeport "
- Comp & Benefits
- Work/Life Balance
- Senior Management
- Culture & Values
- Career Opportunities
I worked at BASF Corporation full-time (more than an year)
Excellent community. All staff at the BASF Freeport site are friendly and willing to lend a hand to help. A Team mindset helps to excel at this site. BASF as a whole along the Louisiana to Texas Gulf Coast is rumored to be reevaluating salary and possible raises are coming. Excellent opportunities to come in the near future with openings becoming available due to retirement of senior employees.
The company is beginning to feel the pressure of what some call the "silver bullet", where an age gap has been created between senior employees and junior employees. Basically, there is a majority of really experienced senior employees and really novice junior employees, with very few mid-experienced employees. This "silver bullet" really kicks in when the senior employees retire and all there valuable experience is lost, and the junior employees are not quite advanced enough to fill the role left by the retired seniors.
Assign one or more senior employees to mentor junior employees. Knowledge transfer is accelerated by the dual accountability.
311 Other Employee Reviews for BASF Corporation (View Most Recent)Sort: Rating Date
I have been working at BASF CorporationPros
Being a research focused company, I, even as a recruiter, am constantly learning from my hiring managers.Cons
It is a large global matrixed organization, you must be someone who can manage through this type of structure.Advice to ManagementAdvice
Continuous communication is essential for employees to continue to remain connected to management.RecommendsApproves of CEO
"Analyst "
- Comp & Benefits
- Work/Life Balance
- Senior Management
- Culture & Values
- Career Opportunities
I worked at BASF Corporation full-timePros
Great company, flexibilty, work life balance, alot of incentives, etc..Cons
Alot of overtime, managers can micro manage you.Work was constantly being pushed around to others, no structure, long, unpaid overtime, issues of disorganization and confusion seem to be caused by upper management,Advice to ManagementAdvice
Communication is key. How about working together as a team. Deligagate work more evenly.RecommendsNo opinion of CEO


text:
Skip to Main Content
IEEE membership options for an individual and IEEE Xplore subscriptions for an organization offer the most affordable access to essential journal articles, conference papers, standards,
eBooks, and eLearning courses.
Learn more about:
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In this paper, we propose the clock-sampling mutual network synchronization (CSMNS) as a non-hierarchical and mutual network synchronization algorithm for wireless ad hoc networks. CSMNS shows superior performance to the IEEE 802.11 timing synchronization function in terms of accuracy, scalability and robustness. An overall view of the differences between the two approaches is presented. CSMNS is compatible with the beacon messages used in the IEEE 802.11 standard, and it is PHY transparent. CSMNS-RMN (rotating master node) is proposed in order to further reduce beacon collisions and overhead. Stability, is a factor that must be considered in CSMNS. However, values of the proportional gain below 0.3 suggest a good stability performance. The use of larger Cmax values in more dense networks and/or the use of techniques that randomly prioritize the transmission of beacons can further reduce the overhead and risks of instability.
A not-for-profit organization, IEEE is the world's largest professional association for the advancement of technology.© Copyright 2014 IEEE - All rights reserved. Use of this web site signifies your agreement to the terms and conditions.


text:
How to Make a French Fry Out of (Almost) Any Vegetableby Robin Miller in Robin's Healthy Take, August 3, 2013
When you think french fries, you think potatoes, right? But who made spuds the king of the fry? Turns out, lots of delicious vegetables make great finger food, and there's no need to deep-fry!
One recipe, endless possibilities. The instructions below work for any and all of the following vegetables:
• Zucchini and yellow squash: unpeeled and cut into rounds or fries
• Avocado (left): pitted and peeled; cut into wedges, dipped in flour, then egg whites and then seasoned bread crumbs
• Portobello mushrooms: stems removed; cut into thin strips
• Yellow Onion: very thinly sliced into 1/8-inch-thick rounds
• Carrots: peeled and cut on a diagonal for oval pieces or cut into sticks for fries
• Butternut squash: peeled and cut into wedges or fries
And of course:
• Yukon gold and red potatoes: peeled or unpeeled; cut into wedges or fries
• Sweet potatoes: peeled and cut into wedges or fries
Baked Vegetable Fries
Preheat the oven to 400 degrees.
Coat a large baking sheet with cooking spray.
Cut the vegetables into uniform sizes.
Arrange the pieces on the prepared baking sheet, in a single layer.
Bake for 20 for 30 minutes, until golden brown and crisp.
Robin Miller is a nutritionist, host of Quick Fix Meals, author of "Robin Rescues Dinner" and the busy mom of two active little boys. Her boys and great food are her passion. Check her out at www.robinrescuesdinner.com.
Similar Posts
Pantry Raid! 10 Healthy Ingredient SwapsWhich ingredients to choose — and which to lose? Here's a quick guide to revamping the pantry and sizing up other common kitchen staples. ...
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text:
Welcome to Alternative Energy Guide
Cultural Impacts Of Alternative Energy In Society Article
This is a selection among article about Cultural Impacts Of Alternative Energy In Society. For a permanent link to this article, or to bookmark it for further reading, click here.
Self Sufficient Alternative Energy: The Only Option for the Futurefrom: Forsgrens
During our time, we have each experienced and observed the importance of energy to our civilization.
In fact, energy is what our current civilization is centered upon. We need it to run our technology.
It is what separates us from the Stone Age.
But our current method of energy production has proved costly.
The fossil fuels we use are slowly poisoning the world we live in, killing the very civilization we hope to strengthen.
Another disadvantage of using fossil fuel is that the supply is limited. Even now, the reality of its limits is showing itself through ever-increasing prices.
That, in essence, drove men to discover self-sufficient alternative energy.
After all, need does drive innovation.
When we needed a better answer to our energy needs, we came up with the idea of self-sufficient alternative energy.
What is self-sufficient alternative energy?
Self-sufficient alternative energy is a type of energy that is virtually unlimited.
This is due to the fact that the sources of self-sufficient alternative energy are constantly replaced by natural processes.
Although fossil fuels are also replaced by the natural processes of the earth, it takes time, a lot of it.
However, the sources of self-sufficient alternative energy are replaced incomparably quickly.
Furthermore, the natural processes that drive self-sufficient alternative energy, is self-sufficient.
Where nuclear power and fossil fuels need special processes to transform them into energy, self-sufficient alternative energy needs only to be harnessed using technology.
The raw power of self-sufficient alternative energy is enough to drive industry.
There are also the environmental advantages of self-sufficient alternative energy.
Self-sufficient alternative energy does not produce any pollution. Unlike fossil fuels, the processes that drive self sufficient alternative energy, does not create byproducts that destroy nature.
They are, after all, created by nature itself.
Is it not funny that Nature itself provided us with the means to protect itself?
We are now beginning to realize that Nature is the source of self-sufficient alternative energy, and that we don't need to destroy it to fuel our civilization.
We don't really need to create chaos to bring order.
Self sufficient alternative energy is powered by nature itself; wind, sun, water, decay, heat, and pressure.
We learned that these provide the power necessary to drive generators that provide energy.
We have discovered ways to create clean-burning fuel out of the byproducts of natural biological processes.
Isn't self-sufficient alternative energy great?
We only need the right technology, and with time, we can find it.
Some people, however, seem to try and stop the progress of self-sufficient alternative energy.
These people are the ones that profit from the business of fossil fuels.
They do everything in their power to limit the funding and resources for the discovery of self-sufficient alternative energy.
Take the water-fueled engine, it has already been discovered, but governments often do not want to fund inventions like this because it threatens the security of oil trade.
And we know that self sufficient alternative energy would threaten that great oil trade even more.
However, some people see the potential of self-sufficient alternative energy.
They realize that, sooner or later, we have to run out of oil and coal.
But the wind, sun, and oceans will still be there; providing self sufficient alternative energy for our needs.
If we indeed wish to have a future, then self-sufficient alternative energy is the only way to go.
Unless, of course, someone actually discovers cold fusion.
Cultural Impacts Of Alternative Energy In Society News
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Sit down if you're not already and I'll hold your virtual hand as I walk you through this one. Sixty-year-old Ohio woman Valerie Spruill made a horrifying discovery after her husband Percy passed away: that he was actually her father. HOLYSHITOMG, I know.
You're probably wondering, as am I, how this is possible. Here's how it went down: Valerie was raised by her grandparents from the age of three months on. Her mother Christine, who was a "night lady" and put away for sex charges in 1980, got together with her father Percy when she was only 15. The pair had seven children together, including Valerie, and Valerie suspects she has more siblings out there. Keep reading »


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Originally written on 5TH QUARTER MAGAZINE | Last updated 11/10/14
Y! Sports reports that Los Angeles Lakers point guard Steve Nash is battling a nerve irritation in his left leg. That seems to be the main reason why his return to the lineup has been delayed. Apparently, Nash's leg fracture has been healed for the past month. The whole nerve irritation is what has been holding him back. Nash has been keeping up with his handles and his conditioning, but cannot participate in practices just yet. Any major pressure on the leg could set him back even more. For now, all the dismaying Lakers can do is wait for Steve Nash to become completely healthy. Pushing him to return too early could just lead to more problems. Lakers head coach Mike D'Antoni has made his intentions clear that he really wants his floor general back soon to run the show for the purple and gold. With Kobe playing point guard duties instead of being a shooter, that is placing more strain on the team. When Nash comes back, Kobe can just float around to an open spot and shoot away. There is no set timetable for the Canadian point guard to return, but there is some wind that he could be back in a Lakers uniform by the end of the month. From a fan's perspective, hopefully he is able to suit up for their Christmas Day game against the New York Knickerbockers, a team that was seriously pushing to acquire him.
Original Story: http://www.5thquartermag.com/2012/12/...
PLAYERS: Steve Nash
TEAMS: Los Angeles Lakers
TEAMS: Los Angeles Lakers
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Smart design.
Books everywhere.
Mending is not something we – as a culture – spend a lot of time doing these days. Fast fashion and mass consumerism has taught us to simply throw older or imperfect items away and replace them with newer versions. I am all for the "Sewing Schoolyard" – let's teach ourselves and our kids to mend – a satisfying task.
My favorite, 10-year old tea towels have seen better days; but, I just can't find the perfect replacement. I use our Alabama Chanin Tea Towels for most kitchen tasks but these have just given me so much kitchen love that I can't bear to part with them.
In perfect wabi-sabi style, Olivia – our Studio Assistant (and budding pattern maker) – mended my old tea towels using scraps of our organic cotton jersey and Button Craft thread. Using applique in combination with seed, whip and eyelet stitches, she repaired the holes and covered the stains. Perfect.
From page 51 of Wabi-Sabi for Artists, Designers, Poets & Philosophers:
"Beauty can be coaxed out of ugliness,
Wabi-sabi is ambivalent about separating beauty from non-beauty or ugliness. The beauty of wabi-sabi is, in one respect, the condition of coming to terms with what you consider ugly. Wabi-sabi suggests that beauty is a dynamic event that occurs between you and something else. Beauty can spontaneously occur at any moment given the proper circumstances, context, or point of view. Beauty is thus an altered state of consciousness, an extraordinary moment of poetry and grace."
Our newest DIY Kit:
Reverse Applique Rose Tank Dress
Perfect for every occasion, this 100% organic cotton jersey tank dress from Alabama Studio Style uses a Rose Placement Stencil from Alabama Stitch Book patterned all-over the garment front and back. Choose your own fabric and thread colors .
Shown here in dark grey with slate thread.
While working on my own wabi-sabi this week, I came across the work of friend Carolyn Strauss and her partner in slowLab – Alastair Fuad-Luke – on page 30-31 of Simply Imperfect: Revisiting the Wabi-Sabi House.
I was reminded of the importance of these six principles:
Introducing our Knotted Necklaces – which are also a great belts.
Shown below styled with our:
Anna's Garden Embroidered Tank and Paisley Skirt
I have immersed myself in Wabi-Sabi for Artists, Designers, Poets & Philosophers over the last weeks and these three, short sentences on the nature of the universe (see pages 46-47) make me so happy:
1. All things are impermanent.
2. All things are imperfect.
3. All things are incomplete.
To me, this seems the essence of wabi-sabi. When I read these, it is like I have been given the okay to just be me today, and every day. Sigh, what a relief.
I made it! 50 years old and going strong.
On my daughter Maggie's birthday each year, I send (or do my best to send) an invitation to celebrate that includes the following text. Today, the invitation is for me:
"Join us in celebrating 50 years of life.
No presents please, plant a flower or a tree for me."
Thank you for all your support for Alabama Chanin… and me.
As my father reminded me: "This is going to be the best decade of your life!"
P.S: For those of you who have been asking, my cleanse was a success – or should I say a beautiful and permanent change of lifestyle: 25 pounds lighter and I feel 10+ years younger.
Now, on to cleansing my life, home and studio! It is going to be a wabi-sabi life – starting today…
In honor of 9/11, print out the PeaceBuilder Pledge below and post it in your place of business, community, kitchen, office, local bar, post office, coffee shop, hair salon, and place of worship. Print it as a post card, send it out, and make it your social media status.
Send us pictures from your actions and we will add them to our Facebook page:
The PeaceBuilder Pledge:
I am a peace builder.
I pledge to praise people, to give up put downs, to seek wise people, to notice and speak up about hurts I have caused, to right wrongs and to help others.
I will build peace at home, at school, (my work place), and in my community each day.
If you are interested in adding PeaceBuilder's to your child's school curriculum, you can contact them here.
(And thank you to Olivia for these lovely actions!)


text:
Abstract available in
Claims available in
Description (OCR text may contain errors)
0% 1974 TAKERU HlGUCHl 3,843,505
ION-SELECTIVE ELECTRODES FOR ORGANIC IONS Filed June 26, 1970 '5 Sheets-Sheet 1 25a FIG.
v mvmvron TAKERU HIGUCHI BYMQM d. 1974 TAKERU -ucaucm 3,
ION-SELECTIVE ELECTRODES FOR ORGANIC IONS I 7 Filed June 26, 1970 I I Sheets-Sheet 2 I RESPONSE OF PVC-'00P A MEMBRANE T0 QUATERNARY AMMONIUM nous Elmv) 2o 4.0 5.0 \ogEQucEl A-TETRAPROPLYAMMONIUMISLOPE=-57.5- B-TETRAPENTYLAMMONIUMISLOPE=59.5 I c- TETRAHEXYLAMMONlUMISlDPE=-58.5
RESPONSE OF PVC-AMIDE MEMBRANE TO TETRABUTYLAMMONIUM BROMIDE m V DISTILLED WATER SLOPE 59.0 40
v INVENTOR log ETBAfl TAKERU HIGUCHI ATTORN I 1974 TAKERU HIGUCHI $843,
ION-SELECTIVE ELECTRODES FOR ORGANIC IONS Filed June 26, 1970 5 Sheets- Sheet s RESPONSE OF PVC-DOP MEMBRANE TO 'TETRABUTYLAMMONIUM BROMIDE IN DISTILLED WATER E (mv) 24o- 200- SLOPE= 59.0
IZO l 1 log [TBAJ RESPONSE OF PVC-DOP MEMB-RANE TO TETRABUTYL AMMONIUM BROMIDE v IN 0.|NKBr,O.lN KH2P04 240 F G. 4 E(mv) 200 eo I v L TAKERU HIGUCH! ATTORN S Oct. 22, 1974 TAKERU HIGUCHI 3,843,505
ION-SELECTIVE ELECTRODES FOR ORGANIC IONS Filed June 26, 1970 5 Sheets-Shet 4 TITRATION 0F DEXTROMETHORPHAN-H Br with SODIUM I TETRAPHENYL emou SAMPLE- 50m 5x IO'3MDMH Br, 0.02M N6, 000mm NH* TITRANT- mo M NoTPB 3 PVC-AMIDE INDICATING ELECTRODE E (mv) I l l l0 I5 20 25 ml NoTPB TITRANT TAKERU meucm o 1974 TAKERU HIGUCHI 3,843,505
ION-SELECTIVE ELECTRODES FOR ORGANIC IONS Filed June 26, 1970 I 5 Sheets-SheetE FIG? -|eo- 5 (my) RESPONSE OF NYLON-PHENOL MEMBRANE 1o souuM TETRAPHENYLBORON SLOPE FOR LOWEST (DNCENTRATIONS 50.5
log ETPBJ RESPONSE OF NYLON-PHENOL E(mv) MEMBRANE T0 TETRABUTYLAMMONIUM E BROMIDE M log ETBAiI INVENTOR TAKERU HIGUCHI United States Patent 3,843,505 ION-SELECTIVE ELECTRODES FOR ORGANIC IONS Takeru Higuchi, 2811 Schwarz Road, Lawrence, Kans. 66044 Filed June 26, 1970, Ser. No. 50,070 Int. Cl. G01n 27/46 US. Cl. 204-195 M 19 Claims ABSTRACT OF THE DISCLOSURE Concentrations of hydrophobic organic ions in aqueous solution are measured with an electrode having a polymeric membrane containing a plasticizer capable of solvating the desired ionic species. The membrane is in electrical contact with and envelopes an internal reference electrode, and this assembly is then used in connection with an additional reference electrode to make potentiometric determinations of ion concentration. The subject electrodes may be made selective toward either organic cations or anions by proper choice of the polymer-plasticizer system.
BACKGROUND OF THE INVENTION This invention relates to the measurement of the concentration of ionic species in solution, and more particularly to a method for determining the activity or concentration of organic ionic species and novel apparatus for use in such determination.
For the electrometric determination of ionic concentrations in solutions, a number of devices are known, and typically include a reference electrode and an ion-selective electrode which when simultaneously immersed into the same body of solution, constitute an electrochemical cell, across the electrodes of which a potential develops approximately proportionately to the logarithm of the activity or the concentration in the solution of the ions to which one of the electrodes is sensitive. An electrometric device, usually either a direct reading circuit or a nullbalance potentiometric circuit is employed for measuring the EMF between the electrodes.
The degree of selectivity of such ion-selective concentration electrodes may experimentally be determined normally by utilization of the Nernst equation:
[outside of the electrode membrane] [inside of the electrode membrane] where E is the potential of the membrane system when the concentrations on both sides of the membrane are equal, E is its potential under the particular conditions of the experiment, 2.303 is the conversion constant from natural logarithms to base-ten logarithms, R is the gas constant, F is the Faraday constant equal to 96, 489 coulombs, n is the number of electrons transferred in the half-reaction, and T is the absolute temperature. At constant room temperature (25 C.) the equation reduces to E: E0 .059 [outside of the electrode membrane] n [inside of the electrode membrane] rapidly expanding areas in analytical chemistry. Most notorious of this type of electrodes are those sensitive to hydrogen. Hydrogen-sensitive electrodes have been formed of such materials as iridium, antimony, quinhydrone, platinum-hydrogen and most commonly, glass of special composition. As a more recent development, it has been discovered that glass electrodes sensitive to ions other than hydrogen, such as sodium and potassium, can be made from various specially adapted glass compositions. See, for example, US. Pats. No. 2,829,090 and No. 3,041,- 252. The mechanism by which the glass electrodes function is believed to be an ion exchange phenomenon taking place at the interface between the glass and the solution under test. Thus, the fact that the sensitivity of glass electrodes is primarily limited to monovalent ionic species has been postulated to be a result of the rigid and solid structure of the glass membrane. It is believed that the mobility of ions having a valence greater than one is limited in glass even though ion-exchange sites adequate both spatially and electrically are present. Moreover, it has been theoretically urged that glass electrodes cannot exhibit anionic selectivity.
Based upon the theory that electrode selectivity results from ion-exchange phenomena, several more recent developments have been directed toward providing an ionexchange interface between an organic ion-exchange liquid and the aqueous test solution. By so doing, it is possible to achieve selectivity toward a greater variety of polyvalent ions by virtue of the increased ion mobility afforded in the liquid ion-exchange medium. In such selective electrodes, the organic and aqueous phases may be directly adjacent to one another, but most often a barrier in the form of a porous membrane or plug is placed between the two liquids. This barrier acts generally to confine the ion-exchange liquid, while at the same time it allows sufficient quantities of the aforesaid liquid to permeate therethrough in order to achieve an organicaqueous interface at the outer, i.e. aqueous side of the barrier surface. In addition to providing selectivity toward a greater variety of polyvalent cations, the liquid ion-exchange electrodes apparently allow for the selective determination of various inorganic anionic species as well.
In an improved version of the liquid ion-exchange type electrode, the aqueous electrolyte solution surrounding the internal reference electrode has been eliminated through the use of a solid state internal reference electrode employing two layers of fused salt coated on a metallic element. See for example, US. Pat. No. 3,502,- 560.
Thus, while significant advances have been made in the development of ion-selective electrodes by which the activity or concentration of both monoand poly-valent inorganic cations, as well as inorganic anions may be determined, the resultant electrodes are based on ion-exchange theory and do not have the capability of rendering selective determination of the activity or concentration of hydrophobic organic ionic species in solution.
SUMMARY OF THE INVENTION Accordingly, it is one object of this invention to provide an improved method and apparatus for the electrometric determination of the concentration of activity in aqueous solution of hydrophobic organic ionic species, especially those containing large hydrocarbon moieties.
Another object of this invention is to provide a method and apparatus for the electrometric determination of the concentration or activity in aqueous solution of hydrophobic organic anions as well as hydrophobic organic cations.
It is a further object of this invention to provide a method and apparatus for the electrometric determinaknown, yet this field represents one of the most tion of the concentration or activity or organic ions in aqueous solution, which method and apparatus is unresponsive to the usual inorganic ionic species present.
In accomplishing these objects, one feature of this invention resides in an electrode for use in measuring the concentration of organic ionic species in an aqueous phase which comprises a polymeric membrane having dispersed therethrough a plasticizer capable of acting as a selective solvating agent for said ionic species, and an internal reference electrode element in electrical contact with and enveloped by the polymeric membrane.
Other objects, features and advantages of the invention will become more apparent from the following description of the invention and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS In the drawings:
FIG. 1 is a diagrammatic cross-sectional representation of an electrode formed according to this invention.
FIG. 2 illustrates a cell assembly utilized for making electrometric determinations in accordance with the present invention.
FIGS. 3-8 are typical Nernst response plots obtained by the method and apparatus of this invention.
FIG. 9 is a titration curve obtained by using an ionselective electrode according to this invention.
DETAILED DESCRIPTION OF THE INVENTION In accordance with this invention a novel method and apparatus has been developed for the potentiometric determination of relatively hydrophobic ions, including both organic cations and organic anions. The underlying theory of the invention is not based on ion exchange phenomena, but rather resides in the discovery that the foregoing ionic species will selectively partition into organic environments such as those offered by plasticized polymers wherein the plasticizer component comprises suitable solvating molecules for the organic ions. As the single further requirement, sulficient hydrophobicity must be conferred on the organic ions to overcome the normal hydration energies associated with ions in aqueous phase. Thus, instead of having an exchange of ions at an interface between the test solution and either a solid or liquid ion-exchange medium, the mechanics of the present invention involve absorption by a polymeric membrane of only the ionic species under study with no counter-ion transfer. Consequently, there occurs a change in the electrical potential of the polymeric membrane itself, in contradistinction to the herefore known ion-exchange-based methods wherein the potential difference is interfacially generated.
It is also possible according to the present invention to provide for the selective absorption of either organic cations or organic anions by proper selection of the polymeric membrane material and its plasticizer component. The primary determinate resides in the selection of an appropriate plasticizer, with the choice of membrane material being dictated generally by its compatibility with the chosen plasticizer. It has been found that plasticizers which have shareable electron pairs preferentially solvate organic cations, while those having acid hydrogens favor transfer of organic anions. In addition, the most highly specific responses are achieved where a highly functional, i.e. bi, tri or polydentate solvating agent is employed.
The ion-selective electrodes made according to this invention are characterized as having a standard reference electrode, e.g. calo-mel enveloped by the selectively permeable polymeric membrane described hereinabove. Electrical contact is provided between the standard reference electrode and the membrane, as for example by an internal reference solution. Alternatively, a solid state internal reference electrode may be employed whereby electrical contact with the piasticized membrane is provided through the fused salt layers of the reference electrode.
A typical, but non-limitative embodiment of the present ion-selective electrode is illustrated in FIG. 1 of the drawings. In this embodiment electrode 20 consists of an electrically insulating container means in the form of glass tube 21 having an opening at each end thereof. To the lower end of the tube there is sealed a selectively permeable, plasticized membrane 22 which, as heretofore described, selectively absorbs organic ions from the test solution. Membrane 22 is held in place by suitable constrictive means 23 such as an elastic ring or alternatively plastic tape of polytetrafluoroethylene or the like. Disposed interiorly of tube 21 and in contact with membrane 22 is a continuous body of ion-containing reference solution 24 such as saturated aqueous NaCl solution or the like. Immersed directly in the internal reference solution 24 is electrode means 25, the portion thereof contacting the liquid 24 being preferably a standard electrode material such as calomel which ordinarily provides a standard junction potential. The upper end of tube 21 may be capped by lid 26 which acts both as a closure and as a support for electrically conductive lead 27 which forms a portion of electrode means 25.
FIG. 2 illustrates a typical cell assembly wherein the subject ion-selective electrodes may be employed. The cell designated generally by reference numeral 30 consists of a suitable electrically insulating vessel 32, conveniently made of glass, into which there is placed a test solution 33 containing the ionic species, the concentration of which is sought to be determined. Placed within the test solution is a first electrode 34 constituting a standard reference electrode such as calomel or the like. The second electrode 20 comprises the ion-selective electrode of this invention as exemplified in FIG. 1. The EMF across the immersed electrodes is measured typically by either a direct reading circuit or a null-balance potentiometric circuit, both of which are well known in the art and need no further explanation.
Apparatus employing the ion-selective electrodes of this invention are capable of measuring the concentration of a wide variety of hydrophobic organic ions, especially those containing large hydrocarbon moieties. Such organic ions include without limitation, quaternary ammonium ions such as tetrabutyl ammonium, tetrapropyl ammonium, tetrapentyl ammonium, tetrahexyl ammonium, alkaloidal cations, such as dextromethorphan cations, morphine cations, diphenhydramine, promazine, phenindamine, mecloxamine, dicyclomine, and others, and as organic anions, tetraphenyl boron, alkyl aryl sulfonates, alkyl sulfates, picrate, perhalocarboxylates, methyl orange, and others. The ion-selective electrodes of this invention respond to such ions in concentration ranges as low as 2 X l0 molar.
Suitable polymeric materials which may be used to form the permeable ion-selective membrane in the electrodes of this invention include without limitation addition polymers such as the vinyl polymers including polyvinyl ehloride, polyethylene, polypropylene, polybutadiene, polyacrylamides, polyacrylates, polyvinylacetate, chloroprene, polystyrenes, polyacrylonitrile, etc.; condensation polymers such as polyamides, polycarbonates, polyurethanes, polyesters, polyethers, etc., and natural resins such as purified natural rubber.
As previously discussed, the plasticizer component dispersed throughout the polymeric material to serve substantially as the major solvating agent for the ionic species under determination is chosen on the basis of its selectivity toward the particular ion, those plasticizers having a shareable electron pair tending to preferentially solvate cations whereas those having acid hydrogens favor transfer of anions. Examples of the former class include, without limitation, fatty amides such as dimethyl oleamide, phthalate esters such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, bis(2-ethylhexyl) phthalate, ditridecyl phthalate, dicyclohexyl phthalate and butylbenzyl phthalate, adipate esters such as bis(2-ethylhexyl) adipate and diisodecyl adipate, phosphates such as triphenyl phosphate, tricresyl phosphate, Z-ethylhexyl diphenyl phosphate, tris(2-ethylhexyl) phosphate and tributoxy ethyl phosphate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, sulphonamides such as N- ethyl o,p-toluene-sulfonamide and o,p-toluene-sulfonarnide, chlorinated biphenyl, polyethylene glycol di-2-ethylhexoate, polyesters, epoxides and the like. The latter class of plasticizers includes without limitation, substituted phenols such as nonyl phenol, oleic acid, stearic acid, perfiuoroacids and the like.
The ion-selective membranes are prepared by incorporating a plasticizer into a compatible polymeric material according to any of the known procedures. For example, polymer in powdered or other form may be dispersed in a quantity of solvent suitable to form a semigelatinous solution upon heating and stirring. To the resulting solution a plasticizer is added and uniformly incorporated by continuous heating and stirring. A thin film of the plasticized polymer solution is then spread on a suitable substrate and allowed to dry, resulting in a thin membrane suitable for use in constructing the ion-selective electrodes of this invention.
It will be appreciated that theoretically there is no lower limit upon the amount of plasticizer to be incorporated in the membrane as even minute amounts will respond to the presence of a selected ion in the adjacent test solution. On the other hand, the upper limit of plasticizer is dictated solely by the practical consideration that a given polymer can accomodate only a given amount of plasticizer before becoming too pliable to be of use in the present application. In practice the amount of plasticizer typically ranges from about 5 to 120 parts per 100 parts of polymeric material. The thickness of the polymeric membrane is more or less a matter of choice, though in practice it will typically range from about to 500 microns.
It will likewise be appreciated that numerous physical relationships of the polymeric membrane to the internal reference electrode are possible. The term envelopd is to be interpreted in its broadest sense to include all physical embodiments ranging from the above described electrically insulating container having a polymeric membrane sealed across one end, to a unitary electrode structure comprising a standard internal reference electrode embedded in a plasticized polymeric membrane.
Selectivity of a given combination of polymer and plasticizer toward a particular organic ionic species is only partly predictable, exact determinations necessarily being made essentially by experiment. Such experimentation is conducted utilizing a cell assembly like that illustrated in FIG. 2 and described in connection therewith. A test solution containing the organic ion to be determined is placed in the cell followed by insertion of the standard reference electrode and the indicator electrode of this invention containing a selected plasticized membrane. When a steady potential is obtained across the two electrodes, the concentration of organic ion in the test solution is gradually increased in predetermined amounts and the change in potential recorded. A truly ion-selective electrode will follow the Nernst relationship, and will thus show a potential change of approximately 59 millivolts for each ten fold change in concentration of the organic ionic species. This relationship may readily be examined by plotting the potential versus the negative logarithm of the ion concentration, and measuring the slope of the resultant plot.
To determine the degree of preferential selectivity of the present electrodes toward organic ions over inorganic ions which may normally be present in a test solution under practical conditions, an essentially identical procedure as just outlined is followed except that various inorganic ions are introduced into the test solution along with the organic ions. Any deviation from the theoretical Nernst relationship indicates interference from the inorganic ions and consequently some electrode selectivity for certain of these ions as well as the organic ion. It can easily be established which inorganic ion or ions are giving rise to the selective response by merely carrying out the foregoing test procedure using a test solution containing only a single inorganic ionic species.
A selectivity constant for a given membrane electrode indicating its preference for the organic ionic species over inorganic ions present can be calculated theoretically according to the Eisenman definition:
where E equals the measured potential, M and M represent the concentrations of the inorganic and organic ionic species respectively, R is the gas constant, T the absolute temperature, F. the Faraday constant, and K the selectivity constant for the given comparative ion pair. A
high value for the constant K. indicates a high degree of selectivity for the organic ion over the inorganic ion.
Specific, but non-limiting examples of polymer-plasticizer combinations and organic ions which are selectively absorbed thereby are:
(l) polyvinyl chloride membrane plasticized with dioctylphthalate for determination of tetrabutyl ammonium cation;
(2) polyvinyl chloride membrane plasticized with dimethyl oleamide for determination of dextromethorphan cation;
(3) nylon membrane plasticized with nonyl phenol for determination of tetraphenylboron anion;
(4) polyvinyl chloride membrane plasticized with dioctyl phthalate for determination of phenhydramine cation.
The ion-selective electrodes of this invention are suitable for application in any of the numerous areas of analytical chemistry where selective determination of organic ionic species is desired. Moreover, by virtue of the very short response periods exhibited by the present electrodes (generally on the order of about 3 seconds), they are ideally suited for use as end-point indicator electrodes in titration procedures.
The following examples will serve to illustrate the invention without in any way being limiting thereon.
Example 1 reparation of an ion-selective membrane.A 10 g. sample of powdered polyvinyl chloride (Bakelite QYKV, Blend 1, Union Carbide) resin is placed in a wedgewood mortar and there is added sufiicient 1,2-dichloroethane solvent to yield a uniform dispersion devoid of any large agglomerates of powder. The dispersion is transferred to a graduated 250 ml. beaker and stirred magnetically while additional solvent is added to the 150ml. mark. The resulting mixture is covered and heated to about 3050 C. Stirring and heating are corginued until a fairly translucent semi-gelatinous solution is obtained. A 10 g. sample of dioctyl phthalate plasticizer (Aldrich Chemical Co.) is then added to the translucent solution with stirring and heating continued for about 1 hour to insure uniform incorporation of the plasticizer in the solution. A thin film of the solution is then applied to a glass plate with the aid of a thin-layer chromatography spreader set at microns, and the film is allowed to dry. Upon drying a thin plastic membrane results which is suitable for the preparation of ion-selective electrodes according to this invention.
An electrode of the type illustrated in FIG. 1 is constructed by sealing the foregoing plasticized-PVC membrane to the end of a glass tube with Teflon tape. Inside the tube is placed a saturated NaCl solution, and a. standard calomel electrode is immersed in the saturated salt solution.
Example 2 Experimental determination of ion-selectivity.-The ion-selective electrode of Example 1 and a standard calomel electrode are placed in a X molar solution of tetrabutylammonium bromide solution in distilled water. An Orion Model 801 digital ionalyser is used to measure the potential between the two electrodes while the concentration of tetrabutyl ammonium cation is raised by measured fiveor ten-fold amounts. A graphical presentation of the potention readings in millivolts plotted against the negative logarithm of the tetrabutylammonium cation concentration is prepared on regular coordinate paper and is represented by FIG. 3 of the drawings. The slope of the plotted curve'is calculated as -59, indicating a theoretical Nernst response of the ion-selective electrode employing a PVC-dioctylphthalate membrane for tetrabutylammonium ion.
Examples 3 and 4 The ion-selective electrode of Example 1 is tested for its selectivity toward inorganic cations by repeating the procedure of Example 2 for test solutions consisting first of potassium bromide in distilled water and then hydrogen chloride in distilled water. The following data is obtained from the two experimental trials:
TABLE I Response of PVC-DO membrane to potassium bromide Cone. KBr (M) Log IK-H E tmv.)
5Xl0' 5. 3 103 5. 0 -86 4. 3 88 4. 0 -91 3. 3 87 3. 0 67 2. (l 42 TABLE II Response of PVC-D01 membrane to 1101 Cone. H01 (M) Log [H+] E (mm) 1X10 5. 0 114. 4.3 'Zfi The procedure of Example 2 is repeated except that each determination of cell potential is made for tetrabutyl ammonium ion in the presence of both potassium and hydrogen ions by maintaining 0.1N concentrations of KBr and KH PO in the test solution. A typical Nernst potential plot of the data, presented in FIG. 4, shows good linearity and a nearly theoretical slope of -58.5, confirming the lack of interference by potassium and hydrogen ions in the selective determination of the tetrabutyl ammonium ion. This is further demonstrated by the following Eisenman Selectivity Constants calculated for tetrabutyl ammonium ion (TBA-H in conjunction with potassium (K+) and hydrogen (H+) ions:
8 Examples 6-8 The procedure of Example 2 utilizing the PVC-dicotylphthalate membrane electrode is repeated for other quaternary ammonium ions. Nernst potential plots of the results are represented in FIG. 5, and the curves show the following slopes:
Curve A-Tetrapropyl ammonium: Slope=57.5 Curve B-Tetrapentyl ammonium: Slope=-59.5 Curve C-Tetrahexyl ammonium: Slope=-58.5
In each instance a Nernstian or nearly Nernstian response is obtained.
Example 9 Using an indicator electrode having a membrane of PVC plasticized with N,N-dimethyl oleamide, the procedure of Example 2 is repeated except that the test solution consists of dextromethorphan hydrobromide in distilled water. FIG. 6 represents a typical Nernst potential plot of the results which has a slope of -59 indicating a Nernstian response of the PVC-dimethyl oleamide membrane for dextromethorphan ion.
Example 10 Using an indicator electrode employing a membrane of nylon plasticized with nonylphenol, the procedure of Example 2 is repeated to determine the response of the electrode to both organic anions and organic cations. FIG. 7 represents the results of a Nernst potential study of the nylon-nonylphenol membrane for its response to tetraphenyl boron anion (sodium tetraphenyl boron in distilled water). From FIG. 7 it is seen that a nearly Nernstian relationship is obtained in the lower concentration range, while deviation from this relationship occurs a higher ion concentrations, probably due to micellarization of the tetraphenyl boron ions.
FIG. 8 demonstrates a total lack of theoretical response of the nylon-nonylphenol electrode to an organic cation, tetrabutyl ammonium.
Example 11 Application as titration indicator electrode:
An indicator electrode of this invention having a PVC- dimethyl oleamide membrane, and a standard calomel electrode are placed in a 50 ml. sample of 5 10 M dextromethorphan hydrobromide, additionally containing a 0.02 M concentration of sodium ion and a 0.001 M concentration of triethyl ammonium ion, i.e., a relatively small organic ion. The sample is then titrated with 0.1 M sodium tetraphenyl boron, and the electrode potential measured with an Orion Model 801 digital ionalyser. FIG. 9 demonstrates that a good potentiometric end point is visible, indicating no interference by the other ions present in the titration.
Thus, this invention provides a practical means for the selective measurement of hydrophobic organic ion concentrations in aqueous solution, a result heretofore unachievable by electrometric means. An ion-selective electrode comprising a reference electrode in electrical contact with and enveloped by a plasticized polymeric membrane is provided. The electrode may be rendered selective toward either organic cations or organic anions by choosing a polymer-plasticizer combination which selectively solvates the desired species.
While there have been shown and described and pointed out the fundamental novel features of the invention as applied to the preferred embodiment, those skilled in the art will appreciate that various modifications, changes, and omissions in the ion-selective electrode illustrated and described can be made without departing from the spirit of the invention. It is the intention, therefore, to be limited only by the scope of the following claims.
an internal reference electrode element in electrical contact with and enveloped by said membrane.
2. An electrode according to Claim 1, wherein said polymer comprises an addition polymer, a condensation polymer or a natural resin.
3. An electrode according to Claim 1, wherein said membrane is from about 10 to 500 microns in thickness.
4. An electrode according to Claim 1, wherein said membrane contains from about to 120 parts of plasticizer per 100 parts of polymer.
5. An electromotive cell comprising:
(1) an electrically-insulating container adapted to contain an aqueous solution which contains hydrophobic organic ions whose concentration is to be measured, said hydrophobic organic ions being selected from the group consisting of hydrophobic organic cations and hydrophobic organic anions;
(2) a standard reference electrode disposed in said container and adapted to be in electrical contact with said aqueous solution; and
(3) the electrode of Claim 1 disposed in said container and adapted to be in electrical contact with said aqueous solution, whereby when an electromotive potential is established between said standard reference e ectrode (2) and said electrode (3), said potential is proportional to the logarithm of the concentration of said hydrophobic organic ions in said aqueous solution.
6. The electrode of Claim 1 wherein said membrane consists essentially of polyvinyl chloride having dispersed therethrough a plasticizer comprising dimethyl oleamide, said membrane being selective in the measurement of the concentration of dextromethorphan cations in aqueous solution.
7. -An electrode according to Claim 1, useful for the selective measurement of the concentration of hydrophobic organic cations in aqueous solution, wherein said polymer comprises polyvinyl chloride and wherein said plasticizer comprises dioctyl phthalate.
8. An electrode useful in measuring the concentration, in an aqueous phase, of hydrophobic organic ionic species selected from the group consisting of hydrophobic organic cations and hydrophobic organic anions, said electrode comprising:
a membrane consisting essentially of a polymer having dispersed therethrough a compatible organic plasticizer capable of solvating, absorbing and transferring said ionic species, said plasticizer being selected from the group consisting of substituted phenols, oleic acid, stearic acid and perfiuoro acids; and
an internal reference electrode element in electrical contact with and enveloped by said membrane.
9. An electrode according to Claim 8, wherein said membrane is from about to 500 microns in thickness.
10. An electrode according to Claim 8, wherein said membrane contains from about 5 to 120 parts of plasticizer per 100 parts of polymer.
11. An electrode according to Claim 8, wherein said polymer comprises an addition polymer, a condensation polymer or a natural resin.
12. The electrode of Claim 11 wherein said addition polymer is a vinyl polymer selected from the group consisting of polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyacrylamides, polyacrylates, polyvinylacetate, chloroprene, polystyrenes, and polyacrylonitrile.
13. The electrode of Claim 11 wherein'said condensation polymer is selected from the group consisting of polyamides, polycarbonates, polyurethanes, polyesters, and polyethers.
14. The electrode of Claim 11 wherein said natural resin is natural rubber.
15. The electrode of Claim 8 wherein said plasticizer is nonyl phenol.
16. The electrode of Claim 8 wherein membrane con sists essentially of nylon having dispersed therethrough a plasticizer comprising nonyl phenol, said membrane being selective for measuring the concentration of tetraphenylboron anions in aqueous solution.
17. An electromotive cell comprising:
(1) an electrically-insulating container adapted to contain an aqueous solution which contains hydrophobic organic ions whose concentration is to be measured, said hydrophobic organic ions being selected from the group consisting of hydrophobic organic cations and hydrophobic organic anions;
(2) a standard reference electrode disposed in said container and adapted to be in electrical contact with said aqueous solution; and
(3) the electrode of Claim 8 disposed in said container and adapted to be in electrical contact with said aqueous solution, whereby when an electromotive potential is established between said standard reference electrode (2) and said electrode (3), said potential is proportional to the logarithm of the concentration of said hydrophobic organic ions in said aqueous solution.
18. An electrode assembly for measuring the concentration, in aqueous solution, of hydrophobic organic ions selected from the group consisting of hydrophobic organic cations and hydrophobic organic anions, comprising a hollow container having an opening therein, a membrane disposed across said opening, said membrane consisting essentially of a polymer having dispersed therethrough a compatible plasticizer capable of selectively solvating, absorbing and transferring said organic ions, said plasticizer being selected from the group consisting of dioctyl phthalate and dimethyl oleamide; an electrically conductive solution disposed within said container in contact with said membrane; and a reference electrode having a stable contact potential disposed in said container and being in electrical contact with said membrane through said conductive solution.
19. An electrode assembly for measuring the concentration, in aqueous solution, of hydrophobic organic ions selected from the group consisting of hydrophobic organic cations and hydrophobic organic anions, comprising a hollow container having an opening therein, a membrane disposed across said opening, said membrane consisting essentially of a polymer having dispersed therethrough a compatible plasticizer capable of selectively solvating, absorbing and transferring said organic ions, said plasticizer being selected from the group consisting of substituted phenols, oleic acid, stearic acid and perfluoro acids; an electrically conductive solution disposed within said container in contact with said membrane; and a reference electrode having a stable contact potential disposed in said container and being in electrical contact with said membrane through said conductive solution.
References Cited UNITED STATES PATENTS 3,429,785 2/1969 Ross 204- L 3,562,129 2/1971 Simon 204--195 M 3,445,365 5/1969 Ross 204195 L (Other references on following page) 1 1 12 UNITED STATES PATENTS Ion-Selective Electrode," NBS special publication 314 3,298,944 1/1967 Luck 204-195 F PP- 3,450,631 6/1969 Bloch et a1. M Pungor et al., Acta Ch1m. Hung, Tomus 41, 1964, pp. 3,655,526 4/1972 Christian 204-195 T 23945- 5 5 OTHER REFERENCES Analytical Chem., Vol. 39, No. 10, 1967, pp. 1056- U.S. Cl. X.R. 1065. 204--1 T TA-HSUNG TUNG, Primary Examiner UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,84 ,5 5 Dated October 22, 1974 Inv nt Takeru Hiquchi It is certified that error appears in the above-identified patent and that said Letters Patentare hereby corrected as shown below:
Page 1, column 1, directly after the zip code in the inventor's address, insert the following:
--Assignor Research Corporation, Lawrence, Kans.--
Signedand sealed this 4th day of February 175.
(SEAL) Attest:
McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents DRM PO-1050 (10-69) USCOMM-DC 60376-P69 w u.s. GOVERNMENT PRINTING OFFICE I! o-su-su,
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November 20, 2014
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Property to let in Margate Drive, Sheffield S4
£450 pcm (£104 pw)
Whiteways Grove, Sheffield S4Property to rent - 3 bedrooms
Offered the market a lovely spacious three bedroom town house situated on Whiteways Grove. The property is ideally located to take advantage of the nearby local amenities, good road and public transport links and within a short distance to Northern ... More details
Note: Distances are straight line measurements
- Meadowhall (1.6 miles)
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Marketed by Blundells - Hillsborough, S6. Call 0114 352 0157£460 pcm (£106 pw)
Woodspring Court, Sheffield S4Flat to rent - 1 bedrooms
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Note: Distances are straight line measurements
- Meadowhall (1.5 miles)
- Sheffield (2.0 miles)
Marketed by Reeds Rains, S35. Call 0114 446 0121