Chemical analysis of

Polymers

By Dhananjay M balbudhe
M.Tech Polymer first year
19POL204
Hydroxyl value
• It is defined as the mg of KOH required to neutralise the amount of acid produced as acetylation (of hydroxyl group) of
one g of polymer sample (when anhydride is used as an acetylating reagent).

1. Determination of acetic anhydride:

Introduce 2-5g of sample with 5 ml acetylating agent ( acetic anhydride- pyridine in 1:7) in round bottom flask attached
with air condensor placed in water bath. Add 10 ml of distilled water through the top of the condenser. Allow the flask to
cool and then rinse the condenser with n-butanol to collect the acid stuck to the wall of condenser. Then titrate the contents
with 0.5 N potassium hydroxide using phenolphthalein indicator. Carry out blank titration also.

OH value of sample Approx.

Weight g
100-200 2
50-100 3
20-50 5

56.1 ×𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐾𝑂𝐻 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 ×𝑒𝑥𝑐𝑎𝑡𝑙𝑦 𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝐾𝑂𝐻

Hydroxyl value = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑖𝑛 𝑔
2. Acetic anhydride in ethyl acetate: Add 2.35 ml of 72% perchloric acid to 150 ml of ethyl acetate in a clean 250-ml glass
stoppered flask. Pipet 8 ml of Acetic anhydride into the flask and allow it to stand at room temperature for at least 30 minutes,
Cool the contents of the flask to 5°C and add 42 ml of cold acetic anhydride, Keep the flask at 5℃ for an hour, then allow the
reagent to come to room temperature. Some yellow color will develop, but the color and anhydride content of the reagent
remain at satisfactory levels for at least 2 weeks at room temperature.

Procedure
Weigh accurately a sample containing from 3 to 4 mM of hydroxyl into a 125-ml glass-stoppered flask and pipet into it
exactly 5 ml of 2 M acetic anhydride in ethyl acetate. Stir the solids or immiscible liquids until they are dissolved. Allow the
reaction to proceed for at least 5 minutes at room temperature. Add 1 to 2 ml of water shake the mixture, then add 10 ml of
3:1 ethyl acetate-water solution and allow the flask to stand for 5 minutes. Titrate with 0.55M sodium hydroxide using the
mixed indicator (1 part 0.1 % netralised aq. Cresol red with 3 parts 0.1 % neutralized thymol blue), and take the change from
yellow violet as the end point and use the difference between the blank V, and the sample titration V, calculate the percentage
of hydroxyl compound in the sample.

Dilute solutions of perchloric acid in various organic solvents have been widely used in non-aqueous titrations. There is no
hazard under the conditions given in the procedure above. Solution acetylated with perchloric acid present, however, should
not be heated, and the sample and blank solutions should be disposed of promptly after the determination completed.
3. Determination by phthalic anhydride

Weigh the sample 10-1.5 g into 50 ml volumetric flask containing 30 to 40 ml of the purified anhydrous pyridine. After
reweighing the solution make it up to volume with pyridine and shake it to mix it thoroughly. Pipet 25 ml of the phthalic
anhydride solution into a clean, dry pressure bottle by means of an automatic Machlett pipet or buret or a Lowy pipet.
Add to this 10 ml of the solution containing the sample. Place the sealed bottle containing the mixture in an air oven set at
100°C and heat it for 1 hour. At the end of this time, carefully release the pressure and add 50 ml of distilled water. After
mixing the solution, cool it under the cold water tap and titrate it immediately with standard 0.35N sodium hydroxide, using
phenolphthalein as an indicator. Make a blank determination in the same manner on the reagents used.

4. By pyrometallic dianhydride

Reagents: Peromellitic dianhydride, 0.5M. Dissolve 109 grams of pyromellitic dianhydride in 525 ml of dimethylsulfoxide and
then add 425 ml of pyridine .Standard 1N sodium hydroxide solution. Phenolphthalein indicator.

Procedure:
Pipet 50 ml of 0.5M pyromellitic dianhydride solution into a glass stoppered 250-ml flask. Weigh a sample containing 0.010 to
0.015 equivalent of alcohol or amine and add to the reagent in the flask. Place the flask on a steam bath, wet the stopper with
pyridine, and seat loosely in the flask. Heat the contents for 15 to 20 minutes (30 minutes for polyglycols). Add 20 ml of water
and continue the heating for 2 minutes Cool the mixture to room temperature and titrate with 1N sodium hydroxide to the
phenolphthalein end point. Titrate a blank, from which only the sample is omitted, in the same manner.

(𝐵−𝐴)×𝑁×17.01
Hydroxyl value= 𝑔𝑟𝑎𝑚𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒.
5. Determination of hydroxyl value in presence of amine group. (For novolac resin)

• Amines react rapidly and quantitatively with anhydrides and in fact can be determined by any of the foregoing methods.
Therefore in samples of hydroxyl compounds containing amine, the esterification methods will determine the total of
hydroxyl plus primary and/or secondary amino groups.

• A direct titration of a separate sample with acid, in aqueous or non-aqueous media, however, will determine the amines.
This amine value can then be subtracted from the esterification analysis to yield the hydroxyl value by difference. Since
the acetylation values and the amine titration values are generally very accurate and precise, the hydroxyl analysis
obtained by difference is generally quite accurate and precise. As the amine content rises and hydroxyl content falls,
however, the difference between the two analyses decreases; thus the accuracy and precision also decrease.

• There is a direct method for determining hydroxyl in the presence of amino groups which consists of acetylating both
groups forming the corresponding esters and amides. The excess anhydride and acetic acid are neutralized, and then
advantage is taken of the fact that esters hydrolyze at a much faster rate than amides. A known excess of methanolic
sodium hydroxide is added beyond the neutral point, and a controlled saponification is run. Many esters completely
saponify before any noticeable amount of amide has reacted. This direct method is not any more rapid than the indirect
method outlined earlier.
6. Hydroxyl Value for polyhydroxy compounds.

The sample is treated with known amount of periodate. After the reaction is completed, potassium iodide and sulphuric
acid are added. Both the residual periodic acid and the iodic acid formed liberate iodine. The amount of ioine liberated is
determined by titration with std. sodium thiosulfate. Therefore, this method is dependent on the slight difference in the
iodine liberated by periodic and iodic acid.

Significance:

• Hydroxyl value of polyol is very important in synthesis of polyol because depending on the molecular weight of polyol
and its hydroxyl value various specialities of Polyurethanes. For example for synthesis of soft adhesive low hydroxyl
value polyol (50-160 mg KOH/g) and for hard adhesives hydroxyl value should be 250-1000 mg KOH/g. Similarly
flexible polyurethanes are prepared long chain polyols with higher hydroxyl value and rigid foams short chain polyols
with low hydroxyl value.

• Also in the depolymerisation of polyurethane, the reaction is monitored by observing hydroxyl value.

Hydroxyl number Polymer

Polyvinyl alcohol 1000-1270
Phenol-formaldehyde 125-450
Acid Value
• Acid number of a resin polymer is defined as the milligrams of KOH required to neutralise the amount of acid
groups present in one gram of polymer. It is expressed as mg KOH/ g of polymer.

Procedure: Weigh accurately 2-4 g of sample depending upon the expected acid content. Dissolve it in 50mL of neutral
methyl ethyl Ketone. Add 2-3 drops of phenolphthalein indicator to the solution. Titrate the solution against the
standard alcoholic KOH solution until pale pink colour appears permanently. If the solvent is not neutral, carry out a
blank titration.

56.1 ×𝑚𝑙 𝑜𝑓 𝐾𝑂𝐻 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 ×𝐸𝑥𝑎𝑐𝑡 𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝐾𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 Acid value of sample Approx.
Acid value = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑖𝑛 𝑔𝑟𝑎𝑚 Weight
56100×𝑛𝑜.𝑜𝑓 𝐶𝑂𝑂𝐻 𝑔𝑟𝑜𝑢𝑝𝑠
100 2.5
Theoretical acid value = 𝑀𝑜𝑙.𝑤𝑡 15-30 5
30-100 1
Significance:

• It is also useful to know the progress of polyesterification reactions.

• In the synthesis of alkyd resin acid value is monitered to keep it as low as possible less than 10 mg KOH.

• If acid value is more reactive pigments may reacts with acid groups giving colour change. It also cause
corrosion, water absorption etc.

Polymer Acid value

Cellulose nitrate 0
PMMA 4
Alkyd resin 5-50
PF Less than 20
Iodine value

• It is defined as the quantity of iodine monochloride in grams reacting with the unsaturated groups present in 100 g of the
polymer. It is expressed as g ICl/100 g resin.

1. Wij’s Method

Dissolve 0.2-1.0 g of the sample in a 250 ml Iodine value flask in 20-50 ml of chloroform or carbon tetra chloride or benzene.
Add 25 ml Wij’s solution. Put a stopper on the flask and keep it in the dark for 30 min. Add 10 ml potassium iodide and 100
ml distilled water to flask. Titrate it using sodium thiosulfate till a yellow colour is obtained. Then add few drops of starch
indicator. The solution becomes dark blue in colour. Continue to titrate blue colour solution. The end point is blue to
colourless. Carry out a blank experiment in a similar manner.
1.269 ×(𝐵−𝐴)
Iodine value = 𝑊

A- vol. of sod. thiosulphate consumed by

sample

B- Vol. of sod. thiosulphate consumed in

blank run.
2. Kaufman method by bromination:

For each liter of solution, 17.2 grams (5.5 ml) of bromine is dissolved in carbon Tetrachloride (25 ml) and water (100 ml) in a
glass-stoppered flask are cooled in an ice bath for 10 minutes. Reagent 15 ml is added and the flask is stored in the dark for 10
min. Potassium iodide solution 15 ml of 20% is added and the titration is made with 0.1 N sodium thiosulfate solution to the
starch end point.

3. Hubl’s method : The reagent is prepared by dissolving 25 g of iodine in 500 ml of nearly absolute alcohol, and 30 g. of
mercuric chloride in an equal volume of the same solvent .The latter solution is filtered, if necessary, and then added to the
tincture of iodine. The mixed solution should be allowed to stand for 12 hours before being used, as, owing to the presence
of impurities owing in the alcohol employed, it is liable to undergo considerable reduction in strength, and must in all cases
be re-standardised immediately before or after use.

To estimate the iodine-absorption, from 0.2 to 0.3 g of drying oil, 0.3 to 0.4 g of non-drying oil, or from 0.8 to 1.0 g, of fat
weighed accurately, and dissolved in 10 ml of chloroform, The solution is mixed in a stoppered flask with 20 ml of the
standard solution of iodo-mercuric chloride, and if the liquid is not quite clear after agitation a further addition of chloroform
is made if the mixture becomes decolorised, or nearly so, after standing a short time, a further addition of 5 or 10 ml of iodine
solution must made. To ensure accurate results, the excess of iodine must considerable, and hence the liquid ought still to be
quite brown after standing for 2 hours.' After that time, from 10 to 15 ml of a 10 % aqueous solution of potassium iodide
should be added and the whole diluted with about 150 ml of water of which is present in the aqueous and part in the
chloroform solution is then estimated by titration with thiosulphate, and starch solution being added just before the end of the
reaction. A blank experiment with the same quantities require to perform.
4. Waller's Method: One drawback to the use of the Hübl solution is that there is a gradual reduction in the amount of free
iodine present .As a remedy against this Waller saturates the iodine solution with hydrochloric acid. His solution is prepared
by dissolving 25 g, of iodine in 250 ml. of 95% alcohol, and mixing the solution with 200 ml. of an alcoholic solution of as
g of mercuric chloride and 25 g of hydrochloric acid and the whole diluted with alcohol to 500 ml.
In a solution thus prepared the iodine shown on titration had only fallen from 49.31 g to 46.60 g in 64 days, while the free
acid had increased to a corresponding extent. In the opinion of Wijs the fact that hydrochloric acid is not set free from the
addition compound, as in Hübl's method, renders it probable that the iodine value obtained when the blank solution is titrated
after the absorption is more correct than the Hübl value, although the difference is slight.

5. Hanus' method: This method is frequently used for determining the iodine value. It differs from the Wij’s method in the
fact that iodine bromide is used as the active agent instead of iodine chloride. The reagent is prepared by adding 13 g of
bromine, drop by drop, to 20 g of finely powdered iodine contained in a flask chilled so that the temperature does not exceed
5° to 8° during the reaction, From 0.1 to 0.7 g the oil or fat dissolved in 10 ml of chloroform is mixed with 25 ml of the iodine
bromide solution, and after 15 minutes, 15 ml of a 10% solution of potassium iodide are added, and the liberated iodine
treated with standard thiosulphate solution.

Comparative determinations of the iodine value, oleic, ricinoleic and undecylic acids, made by by the methods of Hübl’s,
Waller, Wij’s and Winkler, gave practically consistant results. In the case of linolic acid the only method that gave theoretical
results was that of Winkler, the other methods giving; too high values. The iodine values of crotonic, tiglic and cinnami acids
could not be determined by the methods of Hubl, Waller and Wijs wheras nearly theoretical results were obtained by winklers
method.
6. Winkler’s method: From 0.1 to 0.5 g of fat is dissolved in 10 ml of winklers solution(0.5 N potassium bromate solution
containing 1-1.5 g of potassium bromide and 10 ml of 10% hydrochloric acid). After 30 min – 2 hours (according to the
degree of unsaturation of fat) 10 ml of 10% potassium iodide solution are added and the liberated iodine titrated with
thiosulfate solution.

Significance:

• Iodine value estimates the level of unsaturation in compunds.

• Polymers are also likely to contain double bonds in their main chain or may have some residual monomers entrapped in
the matrix. By finding out iodine value it is possible to estimate the presence of unreacted monomers in the polymers.
• It is also useful in estimating the quality of oils and fats.

Oil Iodine number

Non- drying Less than 100
Semi-Drying 100-130
Drying More than 140
Saponification value

• Saponification number is defined as the quantity of KOH (in mg) required to saponify fatty material present in 1 g of
sample. It is expressed as mg KOH/g of sample.

Procedure: Weigh 2-2.5g resin sample to flask and add ethyl methyl ketone or alcohol 50 ml and fit the flask with
condenser and reflux it for 1 hour and titrate it with 0.5 N HCl until pink colour disappears.

56.1 × 𝐵−𝐴 ×𝑁
• Saponification value of the sample = 𝑊
• Ester value = (saponification value)- (Acid value)
Significance

• This experiment confirms the esterification reaction and the extent of esterification can be
studied.

• The saponification value gives an indication of the component fatty acid chains. For example
erucic rapseed oil containing C22 has lower saponification value than linseed oil containing C18
i.e higher the molecular weight of fatty acid lower will be the saponification value.

Polymer Sap Value

UF, PAN, PS 0
Alkyd resin 150-375
PV acetate 100-650
Epoxy value:

• It is defined as the weight of the resin in grams which contains 1 gram equivalent epoxy groups. It is expressed as
100/epoxy equivalent.

• Procedure: Method I- Introduce 0.5 g of resin in round bottom flak and then add 25 ml pyridine hydrochloride
solution which is being attached with air condenser for reflux and allow to cool it. Add ethyl alcohol 20ml . Titrate it
with alc. Potassium hydroxide solution using bromothymol blue indicator. Near the end point. Colour changes from
yellow to green and finally intense blue.

𝑊×1000 100
Epoxy equivalent = and Epoxy Value= 𝐸𝑝𝑜𝑥𝑦 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
𝐵−𝐴 ×𝑁
Method II- Epoxy compound is dissolved in benzene or chlorobenzene and titrated directly with 0.1 N hydrobromic acid in
glacial acetic acid. The end point is determined using crystal violet indicator. It gives good results if particular attention is
given to protecting the reagent in a closed system during storage . This method was adopted by ASTM D 1652-67 .

Significance:

It is useful for determination of molecular weight as well as for the calculation of quantity of amine/amide curing agent
required by the epoxy groups.

Determination of epoxy value also helps in deciding quality and batch consistency of epoxy resins.
Amine Value
• It is defined as the milligrams of KOH equivalent to the amine alkalinity present in one gram of the sample. It is
expressed as mg KOH/ g of polymer.

Procedure:
I) For reactive polyamide
Weigh about 0.3-0.4 g of resin smaple in a conical flask and dissolve the resin by adding 50 ml of glacial acetic acid with 2-3
drops crystal violet indicator and titrate against perchloric acid solution. End point is the change from blue to green.
II) For non-reactive polyamide
Dissolve 3-4 g in isopropyl alcohol (25-30ml), in conical flask and add bromophenol blue indicator. Titrate against 0.05 N
std. HCl acid. End point is the change in colour from green blue to lemon yellow.

56.1×𝑉𝑜𝑙.𝑜𝑓 𝑝𝑒𝑟𝑐ℎ𝑙𝑜𝑟𝑖𝑐 𝑎𝑐𝑖𝑑 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑×𝑁

Amine value = 𝑊

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑒𝑝𝑜𝑥𝑦 𝑡𝑎𝑘𝑒𝑛 ×𝐸𝑝𝑜𝑥𝑦 𝑣𝑎𝑙𝑢𝑒

Polyamide resin required to cure epoxy resin = 𝐴𝑚𝑖𝑛𝑒 𝑣𝑎𝑙𝑢𝑒

𝑁𝑜.𝑜𝑓 𝑎𝑚𝑖𝑛𝑜 𝑔𝑟𝑜𝑢𝑝𝑠 ×56100

Theoretical amine value = 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

𝐴𝑐𝑡𝑢𝑎𝑙 𝐴𝑚𝑖𝑛𝑒 𝑣𝑎𝑙𝑢𝑒

% purity = 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝐴𝑚𝑖𝑛𝑒 𝑣𝑎𝑙𝑢𝑒
Estimation of hydrolysable chlorine content in liquid epoxy resin

The hydrolysable chlorine content in an epoxy resin shows incomplete dehydrohalogenation. This value can be used to
calculate the approximate chlorohydrin group content in the resin. The hydrolyzable chloride content of epoxy resins is a
vital characteristic in deciding their reactivity and the expected properties of coatings made using such resins. The use of
these low-chlorine epoxy resins in the fields of electronics and/or electrical engineering considerably reduces the
components' susceptibility to corrosion.

Procedure:
Take about 6 to 8 grams of the sample to be tested into each of two Erlenmeyer flasks and then pipette out 50ml of 0.1 N
methanolic potassium hydroxide solution into each flask and into two blanks and also Add to each of this 15 ml of
toluene. Stopper the flasks and swirl until the resin is in solution. Add a few glass beads and connect the flasks to a reflux
condenser and place on a hot plate. Reflux the mixture gently for 15 minutes. Allow it to cool to ambient temperature.
After cooling, wash the condenser down with 5 ml of methanol. To this add 3 drops of phenolphthalein indicator solution.
Titrate the mixture with 0.1N hydrochloric acid to the first disappearance of pink colour. The percent hydrolysable
chlorine is then calculated.
𝑉𝑜𝑙.𝑜𝑓 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑×𝑁×35.5×100
% hydrolysable chlorine = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑒𝑝𝑜𝑥𝑦 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠
Carbonyl value

• The carbonyl value is the quantity of KOH in milligrams equivalent to the quantity of hydroxylamine required to
oximate 1 g sample. It is expressed as mg KOH/g of sample.

• Procedure: 0.2-2 g of Sample is dissolved in ethanol but carbonyl free solvent in round bottom flask which is followed
by addition of 50 ml hydroxylamine solution and it is refluxed for two hours and 1 ml bromophenol blue indicator and
titrated against 0.05N NaOH solution with colour change of purple to yellow.

11.22 ×(𝐵−𝐴)
• Carbonyl value = − Acid number
𝑔 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
Isocyanate content

• It is defined as the amount of isocyanate present in 100 g of material. It is expressed as percentage.

• Procedure: Weigh accurately 4-5 g resin sample in a 250ml Erlenmeyer flask. If isocyanate content is less, then weigh higher
quantity of the sample. Add toluene (20ml) to the flask to dissolve the sample. Shake well until all sample gets dissolved.
Add butyl diamino reagent (25ml) and stopper the flask immediately. Allow the solution to stand for 30 min at room
temperature. Add isopropyl alcohol (115ml) and bromocresol green indicator solution (0.5ml) to the flask. Titrate it with the
standard HCl till blue colour of the solution is changed to distinct yellow. Carry out a blank titration.

4.2 × 𝐵−𝐴 ×𝑁
Isocyanate content =
𝑊

A- Vol. of HCl req. for sample.

B- vol. of HCl req. for blank.
Significance:

• Isocyanate content is important in synthesis of Polyurethane elastomers to determine isocyante is prepolymer or not. If
isocyante content of less than 12% is enough to be considered prepolymer.

• Routine determination of diioscyante content is always desirable because diisocyanate is not stored under proper
conditions, gets converted to insoluble urea due to reaction with moisture.

• Moreover dimerization of the diisocyanate may also occur and thus isocyanate is wasted, subsequently diminishing its
active content. Also isocyanate content is important in synthesis of polyurethane .
Chlorine content of PVC resin:

• Chlorine content is the quantity of chlorine present in 100g of sample. It is expressed in percentage.

• It is useful to find out the purity of PVC. PVC contains 56.8% chlorine. Chlorine content of CPVC is 67-69%

• Procedure: In nickel crucible PVC is placed between sodium carbonate and bicarbonate and heated in muffle furnace at
615℃ for two hrs. after heating it is put in boiling distilled water and filter it to separate the non-soluble unsaturated
polymer and titrate the filtered solution against the 0.5 N silver nitrate using potassium chromate as a indicator. End point
is, change of colour from yellow to brick red.
 35.5 ×𝑉×0.5
% of chlorine content =
𝑀

M- Mass of PVC resin.

V- Vol of 0.5 N silver nitrate solution req.
Sulfur content:

A known mass of organic compound containing sulphur is heated withan excess of fuming nitric acid in sealed carius tube.
The whole of sulphur present in the compound is converted into the sulphuric acide which is treated with a slight excess of
barium chloride solution. Thus, barium sulphate gets precipitated. It is filtered, washed, dried, and weighed. From this, the
percentage of sulphur can be calculated.

32 ×𝑀𝑎𝑠𝑠 𝑜𝑓 𝐵𝑎𝑟𝑖𝑢𝑚 𝑠𝑢𝑙𝑝ℎ𝑎𝑡𝑒×100

% of sulphur = 233×𝑀𝑎𝑠𝑠 𝑜𝑓 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

Significance:

1. Testing for the sulfur content in rubber compounds is an important aspect of understanding performance properties.
2. Quantitative sulfur determination is necessary to permit reconstruction of a sulfur-cured rubber formulation.
References:

1. Siggia, “Quantitative organic Analysis Via Functional groups”, 4th Edition.

2. Cheronis N D, “Organic functional group analysis”.
3. Allen, “Commercial organic analysis”.
4. A. Krause, A. Lange, M.Ezrin, “Plastic analysis guide”.
5. D G Hundiwale, “Experiments in Polymer Science”.
THANK YOU!!