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Determination of Iodine Value in Triisocetyl Citrate (Citmol-316) by United

Satates Pharmacopeia Hanus Method

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Y. Yildiz et al, IJCPS, 2019, 7(2): 38–41 CODEN (USA): IJCPNH | ISSN: 2321-3132

International Journal of Chemistry and

Pharmaceutical Sciences
Journal Home Page:www.pharmaresearchlibrary.com/ijcps

RESEAECH ARTICLE

Determination of Iodine Value in Triisocetyl Citrate (Citmol-316) by United Satates

Pharmacopeia Hanus Method
1
Y. Yildiz*, 2M. A. Alfeen, B. Yildiz3
1
Science Department, John F. Kennedy Educational Complex, ACT-Academy AP Chemistry Teacher, New Jersey, USA.
2
Department of chemistry, Faculty of Second Science PhD, Al-Baath University, Homs, Syria.
3
Department of Biomedical Sciences, Rutgers University, Newark, NJ, USA

ABSTRACT
The Iodine value (IV) also called “Iodine number or Iodine absorption value” is an important analytical characteristic of
unsaturation of fats and oils. It is expressed as the “ number of grams of iodine that will react with the double bonds in 100
grams of fats, oils, and waxes.” Saturated oils, fats, and waxes take up no iodine; therefore their iodine value is zero; but
unsaturated oils, fats, and waxes take up iodine. Unsaturated compounds contain molecules with double (-C=C-) or triple (-
C≡C-) bonds, which are very reactive toward iodine. The more iodine is attached, the higher is the iodine value, and more
reactive, less stable. In performing the test, a known excess of iodine, usually in the form of iodine monochloride (ICl), is
allowed to react with a known weight of the oil, fat or wax, and then the amount of iodine remaining unreacted is determined
by titration using of sodium thiosulfate volumetric standard solution.
Keywords: Iodine Value, Hanus method, Triisocetyl Citrate, Citmol-316

ARTICLE INFO

Corresponding Author
Y. Yildiz
Science Department,
Al-Ghazaly Jr/Sr High School AP Chemistry Teacher,
New Jersey, USA.
MS-ID: IJCPS3883 PAPER-QRCODE
A R T I C L E H I S T O R Y: Received 26 Dec 2018, Accepted 29 January 2018, Available Online 27 February 2019
Copyright©2019 Y. Yildiz, et al. Production and hosting by Pharma Research Library. All rights reserved.
This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits
unrestricted use, distribution and reproduction in any medium, provided the original work is properly cited.
Citation: Y. Yildiz, et al. Determination of Iodine Value in Triisocetyl Citrate (Citmol-316) by United Satates Pharmacopeia
Hanus Method. Int. J. Chem, Pharm, Sci., 2019, 7(2): 38-41.

CONTENTS
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2. Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
3. Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .40
4. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .41

1. Introduction
Iodine Value is a useful specification for fats and finds a melting point and hardness. As Iodine value is a measure of
variety of uses. The Iodine Value relates to a range of other the refractive unsaturated bonds it may also relate to
physical characteristics of tallow such as refractive index, chemical characteristics such as oxidative stability and
International Journal of Chemistry and Pharmaceutical Sciences 38
Y. Yildiz et al, IJCPS, 2019, 7(2): 38–41 CODEN (USA): IJCPNH | ISSN: 2321-3132
tendency to polymerize.Triisocethyl Citrate , IUPAC name: 2.2. Reagents
tris (14-methylpentadecyl) 2-hydroxypropane-1, 2, 3- All reagents shall be of analytical reagent quality unless
tricarboxylate, Trade name: Citmol-316, Synonyms: stated otherwise.
triisohexadecyl citrate, 1, 2, 3-Propanetricarbozylic acid, 2-  Recently boiled and cooled distilled or deionized
hydroxy-, triisohexadecyl ester. Triisocetyl citrate is a clear water.
colorless viscous liquid, soluble in Castrol Oil, Mineral Oil,  Chloroform, HPLC Trace Grade, Sigma-Aldrich.
Ethyl Palmitate, Oleyl Alcohol and Ethyl Alcohol-SD 40 CAS Number: 67-66-3. [Caution: Chloroform is a
95%.[1] Specific gravity is 0.908 (at 25oC), flash point is known carcinogenic and highly toxic. Do not
239 oC (closed cup). Triisocetyl citrate has molecular breathe in vapors. Handle with extreme care. Wear
formula: C54H104O7. The structural formula has been shown safety glasses, and gloves. Use in well ventilated
in Figure 1. It contains 54 carbon atoms; the vapor pressure area all the times].
is expected to be extremely low. Citmol-316 will be  Triisocetyl Citrate (Citmol-316) was obtained
hydrolyze in to its components above pH=10 and below from the AKZO NOBEL Chemicals B.V.
pH=3. Hence hydrolysis of Citmol-36 is not expected to  Iodine monochloride, ACS reagent, Sigma-
occur within the environmental pH range due to the low Aldrich, CAS Number 7790-99-0. 1.10 g ±
solubility. 0.1mgI/Cl ratio basis. [Caution: Hanus Solution is
toxic and corrosive. Wear safety glassesand
The Triisocetyl citrate is an excellent pigment binder and gloves].
will be used in cosmetic products including skin care  Potassium Iodide KI, Sigma-Aldrich ACS reagent,
lotions, super moisturizing, lip balms, eye shadows and face ≥99 %, CAS Number 7681-11-0.
powder at a concentration of 4%. [2] Thus the major route of  Sodium Thiosulfate Na2S2O3, (Sigma-Aldrich
exposure of the public to the notified chemical is expected CAS Number 10102-17-7).
to be by dermal contact. 2.3. Solutions
 Potassium Iodide Solution- Dissolve 10.0 g
anhydrous KI in 100 mL of water.
 Sodium Thiosulfate 0.1 N volumetric solution
(VS), prepared by dissolving 24.9 g of sodium
thiosulfate in distilled water and diluting to 1 L.
Accurately standardized VSpotassium dichromate
primary standard as follows normal
standardization procedure.
 Starch Indicator Solution- Mix 1.0 g of soluble
starch with sufficient cold water to make a thin
Figure 1: Structural formula of triisocetyl citrate paste. Add while stirring, to 100 mL of boiling
water. Mix and cool. Use only the clear solution.
2. Experimental 2.4. Method
Several variations of iodine value have been developed,
2.1. Equipment
although Hanus method, Wijs method and Hubl method are
Balance capable of working to the nearest 0.1 mg
still widely used. The iodine number is determinate with a
sensitivity, hotplate, and 500 mL glass stoppered iodine
“carrier” for the iodine, in which case the solution may be
flasks with special wide mouth opening, 50 mL Class A
iodine monochloride in glacial acetic acid (Wijs); iodine
Burette, in 0.1 divisions, with a tolerance of ±0.05 mL, 2
monobromide in glacial acetic acid (Hanus); or iodine-
graduated cylinders capable of containing 50 mL and 100
mercuric chloride in alcohol (Hubl).[3]
mL, 3 mL, 5 mL, and 10 mL. Class A pipets, magnetic
2.4.1. Hanus Method (Titration Method)
stirrer, and 100 mL measuring cylinder. All glassware used
Weight accurately approximately 0.5 g of substance into a
must be clean and dry. Figure 2 described technique of the
250 mL iodine flask, dissolve it in 10 mL of chloroform,
Hanus method in general.
add 25.0 mL of iodobromide TS, insert the stopper in the
vessel securely, and allow it to stand for 30 minutes
protected from, light, with occasional shaking. Then add, in
the order named, 30 mL of potassium iodide TS and 100
mL of water, and titrate the liberated iodine with 0.1 N
sodium thiosulfate VS, shaking thoroughly after each
addition of thiosulfate. When the iodine color becomes
quite pale, add 3 mL of starch TS, and continue the titration
with 0.1 N sodium thiosulfate VS until the blue color is
discharged. Perform a blank test at the same time with the
same quantities of the same reagents and in the same
manner. The difference between the volumes, in mL, of 0.1
Figure 2: Described techniqe of the Hanus method in N sodium thiosulfate VS consumed by the blank test and
general
International Journal of Chemistry and Pharmaceutical Sciences 39
Y. Yildiz et al, IJCPS, 2019, 7(2): 38–41 CODEN (USA): IJCPNH | ISSN: 2321-3132
the actual test, multiplied by 1.269 and divided by the R-CH=CH-R + ICl excess → R-CHI – CHCl-R + ICl
weight in g of the substance taken for test, is the Iodine remaining
Value. Calculate the Iodine Value from formula[5]:
The amount of ICl that has reacted is determined by
( )× × . measuring the amount of ICl remaining after the reaction
Iodine Value = (g I2/ 100 g sample)
has gone to completion.
ICl reacted → ICl excess - ICl remaining
In which 126.9 is the atomic weight form iodine; VB is
titration volume of sample (or standard) and V S is titration
The amount of ICl remaining is determined by adding
volume of sample, in mL, of 0.1 N sodium thiosulfate VS
excess potassium iodide (KI) to the solution to liberate
consumed by the blank test and the actual test, respectively;
iodine, and then titrating with a sodium thiosulfate
N is the exact normality of the sodium thiosulfate VS; and
(Na2S2O3) solution in the presence of starch to determine
W is the weight, in g, of the substance or standard taken for
the concentration of iodine released:
the test. [NOTE-If more than half of the Iodine
monochloride TS is by the portion of the substance taken,
ICl remaining + 2KI → KCl + KI + I2
repeat the determination, using a smaller portion of the
substance under examination] [4] [5].After titration, the
I2 + starch + 2 Na2S2O3 (blue) → 2NaI + starch +
titration assembly is rinsed first D.I water, then with
Na2S4O6 (colorless)
alcohol. It is then gently wiped dry prior to the next
titration. [6]
3.1. Calculation
2.5. Precautions ( )× × .
The sample must be clean and dry. If convenient, a sample Iodine Value = g I2/ 100 g sample
that has been previously tested for moisture by the hot plate .
Normality Factor, (N)= = 0.974
.
method, and has been filtered should be used. All reagents
including the cyclohexane must be fresh. Hanus Solution Test-A.
(Iodine Monochloride) causes severe burns, and the vapors ( . . )× . × .
can cause lung and eye damage. Use in a well ventilated Iodine Value = = 1.2091 g I2 / 100 g
.
area at all times. Do not get in eyes, on skin, or on clothing. sample
Test B. (dup).
( . . )× . × .
3. Results and Discussions Iodine Value =
.
= 1.1075 g I2 / 100 g
The Iodine value (IV) gives a measure of the average sample
degree of unsaturation of the oils, fats or waxes the higher Average of sample result: 1.1583g I2 / 100 g sample
the iodine value, the grater the number of –C=C– double
bonds. By definition the iodine value is expressed as the . .
%RPD= x 100 = 8.77%
grams of iodine absorbed per 100 g of oils, fats or waxes. .

One of the most commonly used method for determining Spiked amount: 0.5 mg/L
the iodine value of oils, fats and waxes is “Hanus Method”. True value : 0.005 mg
The oil or fat to be analyzed is weighed and dissolved in a
MDL study: Average of seven replicates, 0.1 mL reading to
suitable organic solvent, to which a known excess of iodine
burette Na2S2O3 volumetric standard
chloride was added. Some of the ICl or IBr reacts with the . × .
double bonds in the saturated oils, fats or waxes, while the Iodine Value = (0.1) = 0.2 g I2 / 100 g sample
.
rest remains:

Table 1: QC to calculate of Iodine Value

Identity Weight of Net mL of 0.1N Iodine Value
sample (g) Na2S2O3 I2/100 g sample (calculated)
Blank1 -- 55.00 --
Blank2 -- 55.00 --
Test A Sample 0.552 54.46 1.2091
Test B Sample 0.558 54.50 1.1075
Identity Weight of Net mL of 0.1N Iodine Value
sample (g) Na2S2O3 I2/100 g sample (calculated)
Check Std.1.0 mg/L ----- 54.92 0.9888
Spiked(MS) 0.522 54.93 1.6575
Spiked Dup (MSD) 0.525 54.93 1.6480
Table 2: QA to calculate of statistical process
% RPD %RMS %RMSD Ave. % Recovery MDL
8.77 99.84 97.94 98.89 0.2

International Journal of Chemistry and Pharmaceutical Sciences 40

 Y. Yildiz et al, IJCPS, 2019, 7(2): 38–41 CODEN (USA): IJCPNH | ISSN: 2321-3132
4. Conclusion
The relative percent standard deviation for iodine value
determination has been determined to be 8.77% when one
sample was analyzed two times by different chemists on
different days within the same laboratory. 0.5 mg/L Iodine
standard has been added into the sample for percent
recovery. %RMS has been found 99.84% and %RMSD has
been found 99.89 % (Table 1 and Table 2). Specification
iodine value is not more than (NMT) 3.0 g I2/100 g sample.
Results meet the specification of the United State
Pharmacopeia.

5. References
[1] Alzo International, Technical Bulletin # 0639.
Citmol 316, NJ - USA.
[2] National Industrial Chemicals Notification and
Assessment Scheme. Full Public Report.
September 1996. File No: NA/408. Sydney-
Australia.
[3] The chemical and technology of waxes. Warth,
A.H. Second edition, p. 588, 596
[4] Pharmacopeia/National Formulary. U.S. Vol. 1, p.
151
[5] USP 40-NF 35 U.S. Pharmacopeia and National
Formulary <401> Fats and Fixed Oils. Metho I
(Hanus Method). June 1, 2017.
[6] Determination of Iodine Value in Fats and Oils.
Thermo Scientific Titration Application Note No.
H-076
[7] Walker DJ, 1991, Citmol 316 (Tri-isocetyl
Citrate): Fourteen-Day Repeat ApplicationDermal
[8] Irritation Study in the Guinea pig (Non-
Occlusive), Project number 357/1, data on file,
Safe Pharm Laboratories Limited, Derby.
[9] Hagan EC, 1975, Appraisal of the Safety of
Chemicals in Foods, Drugs and Cosmetics.pp 17-
25.

International Journal of Chemistry and Pharmaceutical Sciences 41

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