Abstract
Abstract-The aim of this study was to develop a procedure for preparing film polyelectrolyte complex pectine/chitosan with increased sorption capacity for heavy metal ions which could be used as adsorbent to remove lead (II) ion in waste water. A film of the polyelectrolyte complex between chitosan and pectin were prepared by mixing the complex of both polysaccharides. Firstly, chitosan was grafted with acetate to form carboxymetyl chitosan (CMC). Subsequently, CMC is mixed with pectin to form CMC/pectin film. The result showed that the optimum mass ratio of CMC:pectin to synthesis CMC-Pectin film was 70:30%, optimum adsorbent mass to adsorb Pb (II) was 10 mg with 70% of adsorption and adsorption capacity was 30.1 mg/g. Optimum contact time to adsorb Pb (II) was 75 minutes with 87% of adsorption and adsorption capacity was 40.0 mg/g. Optimum pH to adsorb Pb (II) was at pH 5 with 93% of adsorption and adsorption capacity was 42.7 mg/g. Index Terms-CMC, pectin, CMC-pectin film, adsorbent, lead (II) metal ion.
I. INTRODUCTION
The rapid industrial development and the using of various metallic materials have a negative impact, namely the emergence of cases of environmental pollution caused by waste containing heavy metals [1] . This pollution can cause harm and disturbing people who live around the industry. Refining metal factory, metal plating, painting and manufacture of battery are a source of heavy metal contaminants. Waste containing the remains of these heavy metals are dangerous if not be done properly and the processing is very harmful because it pollutes the environment especially with the nature of the toxicity.
I. INTRODUCTION
Lead (Pb) is one of the major pollutants that contaminate the environment. It happens because the main source of lead pollution is get from motor vehicle exhaust emissions. In addition there is also a lead in industrial wastewater in the production process to use lead, such as battery manufacturing industry, paint industry, and industrial ceramics. The presence of lead in the environment component of the water, soil, and air pollution allowed the development of the transmission became more widely to a variety of living things, including humans, causing health problems, such as the disruption of the synthesis of red blood, anemia, and decreased intelligence in children [2] .
I. INTRODUCTION
Nowadays heavy metals are the environmental priority pollutants and are becoming one of the most serious environmental problems. So these toxic heavy metals should be removed from the wastewater to protect the people and the environment. Many methods that are being used to remove heavy metal ions include chemical precipitation, ion-exchange, adsorption, membrane filtration, electrochemical treatment technologies, etc [3] . Adsorption is one of the physicochemical treatment processes which found to be effective in removing heavy metals from aqueous solutions [4] . According to Bailey et al [5] , an adsorbent can be considered as cheap or low-cost if it is abundant in nature, requires little processing and is a by-product of waste material from waste industry. Adsorption methods are generally based on the interaction of metal ions with functional groups that exist on the surface of the adsorbent through interaction and complex formation usually occurs on the surface of solids which have rich functional groups such as -OH, -NH, -SH and -COOH [6] .
I. INTRODUCTION
Pectin is one of the compounds found in plant cell walls mainland. Pectin, an anionic plant cell wall polysaccharide based on a-(1-4) linked D-galacturonic acid, is commercially extracted from pectin-rich sugar-beet pulp, apple pomace, and citrus peels [7] . All this time, the pectin was widely used in the food industry, pharmaceuticals and cosmetics. At these industries pectin is used primarily as a gelling material [8] . However, when considering that the structure of the pectin component also contains a lot of active groups, the pectin can also be used as a source biosorbent [9] . The main functional groups of pectin are hydroxyl, carboxyl, amide and methoxyl. These functional groups can be used to bind heavy metals, especially hydroxyl groups. Chitosan, a cationic copolymer of glucosamine and Nacetylglucosamine, is a partially deacetylated derivative of a natural polysaccharide -chitin, which is one of the most abundant carbohydrates in nature and is mostly derived from the exoskeleton of crustaceans [10] . Chitosan can be used as an adsorbent because it has amine and hydroxyl groups that can be used as an ion-exchanger, and can act as an adsorbent to adsorb heavy metals. Carboxymethyl chitosan (CMC) is one of the modified chitosan made through esterification process; the product is widely used in the pharmaceutical industry / healthcare and cosmetics. CMC is a water-soluble Interactions occur between polyanions and polycations, leading to the formation of a polyelectrolyte complex (PEC). As a positively charged polysaccharide, chitosan has been incorporated with pectin to fabricate various composite materials [12] and [13] . In addition to ionic interactions, there are other types of interactions that can form between amino groups and carboxyl groups, such as hydrogen bonds and covalent bonds formed using specific conjugating chemicals, like 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (NHS) [14] .
II. MATERIALS AND METHOD

A. Materials
The pectin used was obtained from local pectin from orange peels. And chitosan used was obtained from local chitosan from crab shell.
B. Method
Before use, a first modified chitosan, carboxymethyl chitosan with the workings of the following: Dissolve 3 g chitosan in 80 ml of isopropanol. Add 28 mL NaOH 40% w/v carefully by drops. Chitosan and isopropanol was stirred for 30 minutes.
B. Method
Add as much as 7.65 g of chloroacetic acid, then stirred for 12 hours. The mixture was filtered and washed with ethanol. Dried sediment filtering results in an oven at 600 C for 3 h. g. Carboxymethyl chitosan derived functional group characterized using Infrared spectrophotometer. Once formed CMC, then combined with the following steps:
B. Method
Dissolving 0.2 g of pectin in 10 ml acetic acid 5% v/v were homogenized. CMC dissolving 0.2 grams of acetic acid in 10 ml of 5% v/v were homogenized. CMC and pectin gel mixed and stirred for 2 h. and poured in a Petri dish and dried to the oven for 5 hours at 40 o C. Add 5 ml of 1 M NaOH and let stand for 12 hours. Washing the film with distilled water and then dried to the oven for 2 hours at 40 °C. Obtained adsorbent functional group characterized by using infrared spectroscopy.
B. Method
Synthesis of Film CMC-pectin is done by using a variation of the mass ratio CMC: pectin as in the following Table I . 
III. RESULT AND DISCUSSION
In this study used the absorbent material of pectin and chitosan, because it can be used as a biomaterial that can absorb the metal. Pectin has an active groups of carboxylic and chitosan amine groups. It is a very reactive material that can bind a metal by forming a complex compound. Composite pectin with chitosan forms stable polyelectrolyte complexes [15] . Interaction between active group COO-of pectin and active group -NH 2 of chitosan complement the character of these macromolecules. Its complexes usually have a rigid structure that is very different from its original properties.
A. Characterizations
The film of pectin-CMC was prepared using the membrane method. The FTIR spectra of chitosan (Fig. 1a) show absorption peaks at 3464 cm -1 assigned to the O-H stretching vibration. Width and shift absorption of wave number on -OH group is caused by the overlap -NH of the amine. Absorption robertshah@example.com cm -1 is the stretching vibration of C-H group methylene robertshah@example.com cm -1 is the C-O group. Another Uptake of chitosan look at wave numbers 1651.07 cm -1 indicate the presence of amide groups (-NHCO) [10] and [16] Fig. 1b, CMC shows absorption of peaks IR spectra at wave numbers 3464.15 cm -1 which is the absorption of the -OH stretching vibration that overlap with the -NH stretching vibration absorption. Peak absorption of CH stretching vibration shifted from 2877.79 cm -1 to 2924.09 cm -1 . Increasing the absorption peak of carbonyl bands (stretching C = O) at 1740 cm -1 indicates the addition of a carboxylic group (-COOH) which means it has been formed CMC. From all these data it can be concluded that it has formed CMC result of synthesize chitosan with chloroacetic acid [10] and [16] .
A. Characterizations
FTIR spectra of pectin in Fig. 1c show a broad absorption robertshah@example.com cm -1 , indicates the range of the OH group vibrations. robertshah@example.com cm-1 is the stretching vibration of the-CO -. robertshah@example.com cm -1 is an absorption of group -COOH [17] , [18] and [19] Characteristics of film CMC-Pec using FTIR shows that it has an active force hydroxide (-OH) indicated by the spectra with wave numbers 3464 cm -1 and the active carboxylic group (-COOH) at wave number 1635 cm -1 and bands related to C=O stretching of the ester could be observed at 1751 cm -1 [20] , [21] and [22] . (Fig. 1 d) . Fig. 2 shows the ratio mass between of pectin with CMC. From these Fig the optimum mass ratio between the pectin: CMC is 30%: 70% (Fig. B) showing the greatest intensity of absorption at a wavelength of 3400 (-OH) and 1600 (C = O) and 1700 (-OCH 3 ). 
B. Influence of Mass Ratios

C. Determination of Optimum Adsorbent Mass
The relationship between the mass of adsorbent upon adsorption capacity in Fig. 3 and percentage Pb (II) adsorbed show in Fig. 4 . It shows at 5-10 mg adsorbent mass absorption levels are increasing rapidly due to the growing number of adsorbent process of diffusion and binding of the better adsorbate molecules and adsorbent mass reaches a maximum at 10 mg. At 10-20 mg adsorbent mass absorption levels of Pb (II) adsorbents have decreased due to absorb maximum Pb (II) and the active adsorbent was no longer able to bind Pb (II). From this study, the optimum adsorbent mass obtained was 10 mg with a metal ion concentration of Pb (II) adsorbed at 70% and the adsorption capacity of 30.16 mg/g. 
D. Determination of Optimum Contact Time
The graph of the relationship between the contact time of Pb(II) ion with adsorption capacity and % adsorbed of film and is show in Fig. 5 and Fig. 6 . th minute a perfect mixing occurs so that the films CMC-pectin can absorb Pb (II) optimally. After 75 minutes into a decline due to desorption the metal ion adsorbents release that Pb (II) which has been adsorbed because the pores of adsorbent was saturated by the Pb(II).metal ions Fig. 7 and Fig. 8 show the relationship between pH solution vs. adsorption capacity and the percentage of Pb (II) adsorbed. The degree of acidity or pH of the solution is one of the important factors that determine the performance of the adsorbent in the adsorption process pH value is too low or too high will make optimum adsorbent unable to work. From Fig.  7 be used as adsorbent to remove Pb (II) ion in waste water compared by chitosan or pectin separately.
E. Determination of Optimum pH


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