College of Science

Determination of Ethanol Concentration in Aqueous Solutions

Safety
The amount of unreacted dichromate is then determined by adding potassium iodide solution which is also oxidised by the potassium dichromate forming iodine.

Lab coats, safety glasses and enclosed footwear must be worn at all times in the laboratory. Determination of Ethanol Concentration72 + 14 H+ + 6 I 2 Cr3+ + 3 I2 + 7 H2O Cr2O in The acid dichromate solution needs to be prepared Aqueous Solutions with care. Any concentrated acid spills must be cleaned The iodine is then titrated with a standard solution of up by very carefully diluting with water before wiping sodium thiosulfate and the titration results are used to up. Take care to put the water in the flask first before calculate the ethanol content of the original solution. a flask and adding the acid, and add the acid slowly with constant the alcoholic beverage sample is suspended Introduction in a small container above it (see diagram).The water I S O 2 + 2 I 2 S2O32 + 2 swirling. The flask will gettitration to find the This method uses a redox quite hot. 4 6 and ethanol slowly evaporate and as the ethanol comes concentration of ethanol in an aqueous solution. The in contact with the dichromate it first dissolves, and is Because alcoholic beverages such as wine or beer ethanol is oxidised to ethanoic acid by reacting it with then oxidised. More ethanol evaporates until eventually an excess of potassium dichromate in acid. contain other oxidisable all the ethanol from the beverage has left the sample substances that could interfere Introduction 2 + and reacted with with the titration,transfer the dichromate. Since this the dichromate solution is placed in 2 Cr2O7 + 16 H + 3 C2H5OH it is necessary to the 4 a + 11 H2 titration to This method usesCr3+redoxO + 3 CH3COOH find the takes time, sample in a warmleavetheflask with the beverage sample is suspended a flask and overnight. alcoholic suspended place The amount ethanol in an aqueous concentration ofof unreacted dichromate is then solution. The in a small container above it (see diagram). The water determined by adding potassium iodide solution which ethanol is also oxidised by theethanoic acid byforming Equipment Needed is oxidised to potassium dichromate reacting it with and ethanol slowly evaporate and as the ethanol comes iodine. potassium dichromate in acid. 250 mL conical flaskscontact with the dichromate it first dissolves, and is an excess of in with rubber stoppers burette Cr2O72 + 14 H+ + 6 I 2 Cr3+ + 3 I2 + 7 H2O then oxidised. More ethanol evaporates until eventually 2 + The 2 Cr2 O7 titrated with a+ 3 C2H5OH of iodine is then + 16 H standard solution 5 mL beakers or small glass vials all the ethanol from the beverage has left the sample and sodium thiosulfate and the titration results are used to 4the ethanol11 H2Oof the original solution. beer or wine sample Cr3+ + content + 3 CH3COOH reacted with the dichromate. Since this transfer takes calculate 10 mL and 1 mL pipettes 2 2 time, it is necessary to leave the flask with the suspended 2 S2O3 + I2 S4O6 + 2 I incubator (optional) sample in a warm place overnight. Because alcoholic beverages such as wine or beer
contain other oxidisable substances that could interfere with the titration, the dichromate solution is placed in

Solutions Needed
Acid dichromate solution: (0.01 molL-1 in 5.0 molL-1 sulfuric acid) (see safety notes). Add 125 mL of water to a 500 mL conical flask. Carefully add 70 mL of 250 mL conical flasks with rubber stoppers concentrated sulfuric acid with constant swirling. Cool flask under cold water tap and add 0.75 g of potassium burette dichromate. Dilute to 250 mL with distilled water.

Rubber stopper

Equipment Needed

250 mL Conical flask (wide mouth)

5 mL beakers or Dissolve 1.0 g Starch indicator solution: (1.0% solution) small glass vials of soluble starch in 100 mL of recently boiled water. Stir until dissolved. beer or wine sample
Glass hook

Sodium thiosulfate solution: (0.03molL-1pipettes of 10 mL and 1 mL ). Add 7.44 g Na2S2O3.5H2O to a 1L volumetric flask, dissolve in distilled water and dilute up to the mark. (optional) incubator Potassium iodide solution: (1.2molL-1) Dissolve 5 g of KI in 25 mL of water.

Sample holder

Acid dichromate solution

Method Solutions Needed Method Acid dichromate solution: (0.01 molL-1 in 5.0 molL-1 Sample Preparation Method sulfuric acid)beer samples 1:20 (10 mL inmL of water Sample Preparation notes). Add 125 200 mL) with 1. Dilute (see safety Method

to a 500 mL conical flask. Carefully add 70 mL ofwith Sample water. samples 1:20 (10 mL in 200 mL) 1. Dilute beer distilled Preparation concentratedbeer samples 1:20 (10 mL in 200 mL) with Sample Preparation with constant swirling. Cool distilled water. 1. Dilute sulfuric acid 2. Dilute wine samples 1:50 (20 0.75 1000 mL) with flask under cold water tap and addmL ing of potassium distilled water. samples 1:20 (10 mL in 200 mL) with 1. Dilute wine samples 1:50 (20 2. Dilute beer distilled water. dichromate. Dilute to 250 mL with mL in 1000 mL) with distilled water. distilled water. samples 1:50 (20 mL in 1000 mL) with distilled water. 2. Dilute wine Starch indicator solution: (1.0% solution) Dissolve 1.0 g Titration (described for one beverage) mL) with distilled water. 2. Dilute wine samples 1:50recently boiled of soluble starch in 100for one(20 mL in 1000 water. Stir mL of Titration (described the acidbeverage) solution (see 1. Transfer 10 mL of dichromate distilled water. until dissolved. Titration (describedmL conical flask with matching(see 1. Transfer 10 250 the acid dichromate safety notes) to amL offor one beverage) solution Sodiumnotes) to amLsolution: (0.03molL-1). Add 7.44g(see Titration (describedmL conical flask with matching safety stopper. 250 for one beverage) solution 1. Transfer 10 rubber thiosulfate of the acid dichromate of Na2S2notes) 2to amL 1LmL conical flask with matching(see rubber O3.5H O to250 volumetric flask, dissolve in safety stopper. a 1. Transfer 10 of of the acid dichromate solution 2. Pipette 1 and dilute up to beverage mL the distilled stopper.a 250 mLdilutedthe mark. sample into rubber waterto safety notes) 1 mL of the can be abeverage sample into conical 5mL with matching 2. Pipette the sample holder. This diluted flaskbeaker or glass Potassium iodide solution: of the beverage as theintoKI rubber stopper. of the can(1.2molL-1) beaker or5 g entire the sample holder.samples be abeverage sample of 2. Prepare three This diluted 5mL Dissolve glass vial. Pipette 1 mL in 25 sample holder.samples of the beverage as the entire vial.mL of water. of arediluteda the titration. glass the Pipette 1 mL contents of the flaskthe can beinbeverage sample into 2. Prepare three This used 5mL beaker or contents of holder.samples of the beverage as the entire used a vial.sample the flask arecan bein the titration. glass the Prepare three sample holder5mL beaker or 3. Suspend the This over the Methodof the flaskplaceholdertherubberdichromate contents are used in beverage as vial. Prepare three sample with the titration. the entire 3. Suspend the samples of theover the dichromate solution and hold in stopper (see contentsand hold sample holderthe titration. of the flaskplace with the rubberdichromate are used in over the stopper (see solution 3. Suspend the in figure Preparation Sample1). figure 1). and hold sample holder over the dichromate solution 3. Suspend the in place with the rubber stopper (see 1.4. Store the flask overnight mL2530CmL) with Dilute (10 at in 200 (an incubator figure 1).beer samples 1:20 with the rubber stopper (see solution and hold inovernight at 2530C (an incubator 4. ideal). the flask place Store isdistilled water. figure 1). the flask overnight at 2530C (an incubator is ideal). 4. Store Next morning allow the flask to come to with 2.5.Dilute wine samples 1:50 (20 mL in 1000 mL)room is ideal). morning allow the flask to come toincubator 4. Storewater. loosen the stopper carefully and 5.distilled the flask Next temperature, then overnight at 2530C (an room is ideal).and discardallow the flask to come to room temperature, 5. Next then the sample holder. remove morningloosen the stopper carefully and Titrationand discard the sample holder. remove (describedallow the beverage) to room temperature, then for one stopper carefully and 5. Rinsemorningloosen theflask to come water, 6. Next the walls of the flask with distilled 1.remove and discard the sample holder. solution (see Transfer 10 mL of the acid dichromate temperature, then loosen distilled water and mL of 6. Rinse the wallsmLthethe stopperdistilled1water, then add about 100 of of flask with carefully and safety notes) to a 250 mL conical flask with matching remove and discard mLthedistilled water and 1water, then add about 100 of sample to mix. 6. Rinse iodide solution. Swirlwith distilled mL of potassium the walls theof flask holder. rubber stopper. potassium the wallsmLthedistilled water and 1water, then add about 100 of of Swirl to mix. of 6. Rinse iodide solution.flask with distilled mL acid 7. Prepare 3 blank titrations by adding 10 mL of the 2.potassium iodide solution. Swirl towater and 1into of Pipette 1mL of the diluted beverage sample mL mix. 10 mL of acid then add about 100 titrations by adding distilled 7. Prepare 3 blankmL ofconical flask, adding 100 mL dichromate solution to a be a 5 mL beaker or glass sample holder. This can potassium iodide solution. Swirliodide solution of acid dichromate 3mL of titrations flask, adding 100 mL to a conical adding 7.vial.Prepare 1 three potassium the beverage as the of water andsolutionsamples ofbyto mix. 10 mL and Prepare blank of water to mix. of potassium iodide solution of acid andsolution titrations byflask, adding 100 mL 1 mL to a conical adding 10 mL and dichromate 3 blank swirlingcontents of the flask are used in the titration. 7.entire Prepare swirling to mix. of potassium iodide solution and of water and 1 mL dichromate solution tosodium thiosulfate solution Fill a the sample a conical flask, adding 100 mL 3.8.Suspendburette withholder over the dichromate swirling a mix. with sodium iodide solution and of water toburette of potassiumthiosulfate solution 8.solution each flask place with the rubber stopper Fill and 1 hold and titrateandmL inwith sodium thiosulfate. When swirling toburettecolour fades to yellow (figure When andbrown iodine with sodium thiosulfate solution 8.(seeFill a each flask with sodium thiosulfate. 2), add the titrate mix. figure 1). the brown iodine with andsodium thiosulfate. When and Fill a each flask with keep yellow (figure 2), blue 1 mLtitrateburettecolour fades totitrating until theadd 8. of starch solution sodium thiosulfate solution 4. mL of the iodine colour fades2530C (figuretheadd flask overnight at 1 Store disappears (figures 3-5).totitrating until When the brown each flask with sodium thiosulfate. 2), blue colour starch solution and keep yellow blank flasks Titrate the and titrate (an ofdisappears ideal). 3-5). Titrate the until the blue incubator is (figures keep titrating blank flasks colour starch solution and to results are obtained 1 mL first, and repeat until concordantyellow (figure 2), add the brown iodine colour fades 5.first, ofmorningto (figures flaskTitrate theare obtainedthe Next starch solution and mL). come blank flasks colouragreeing allowconcordanttitrating until the blue (titres disappears within 0.1keep Then titrate each of 1 mL and repeat until the 3-5). toresultsto room temperature, (titres agreeingthen loosen the stopper the beverage do first, and repeatto within 0.1 mL). results blank flasks alcoholdisappearsIf(figures 3-5). Titrate of carefully andthe the three samples titrate each of colour samples.until concordant Thentheare obtained removeconcordant concordant results are will need to and discard the sample holder. alcohol samples.untilresults, mL). Thenof the beveragethe If the three samples titrate each of (titres agreeing to within 0.1 further samplesobtained do not give repeat first, and not givesamples. ofthe three further samples will needdo alcohol concordant results, with distilled water, then be prepared. (titres the walls If the flask samples titrate each of to 6. Rinseagreeing to within 0.1 mL). Thenof the beveragethe be prepared.100 mLthe distilled water of the beverage do not givesamples. If of three further samples will need to alcohol concordant results, samples and add about be mL of potassium results, further samples mix. not give concordant iodide solution. Swirl to will need to 1 prepared. 7.be prepared. Prepare 3 blank titrations by adding 10 mL of acid dichromate solution to a conical flask, adding 100 mL of water and 1 mL of potassium iodide solution and swirling to mix.

Figure 1 Experimental setup for Figure 1 Experimental setup oxidation of ethanol. Conical flask Figureoxidation of ethanol. for 1 Experimental setup for contains yellow acid dichromate oxidation of ethanol. Conical flask Conical flask contains for Figure 1 Experimental setupyellow solution andethanol.dichromate with rubber contains yellowsealedConical flask oxidation of is acid solution and acid Figure 1dichromate setuprubber stopper.Experimentaldichromate Small beaker containing solution yellowsealed with for contains andwith rubber stopper. is sealed is acid oxidationsample is suspended above beverageSmall beakerConical flask stopper. of ethanol. with rubber solution and is sealed containing Small yellow containing contains beakeracid stopper. above from hook in rubber dichromate beverageSmall beaker containing sample is suspended stopper. and sample is suspended beverage solution in is sealed with rubber from hook rubber stopper. above beverageSmall beaker in rubber stopper. from hook containing above sample is suspended from hook in rubber stopper. above beverage sample is suspended stopper. from hook in rubberthe iodine Figure 2 Titration of stopper.

Figure 2 left flask of the formed. TheTitration shows the Figure 2 Titration of the iodine brown-coloured flask shows flask iodine formed. the iodine formed. The left solution resulting Figure 2 Titration ofThe left the from theThe left flask shows the showsformation the brown-coloured brown-coloured solution resulting formed. Titration of of iodine. The Figure 2 formation of the brown the iodine right flask showssolution resulting how from The from the resulting iodine.the solution brown-coloured flask shows the formed. The to how colour fades leftpale of theThe the right the formation yellowbrown formation of iodine. as The from flask showssolution resulting iodine. right brown-coloured with thiosulfate iodine isshows pale yellowbrown colour fades to how the as the flask titrated of iodine. The right flask shows how thebrown fromis is titrated at which starch (this the formation yellow as the stage iodine fades to palepale yellow colour the showsto thiosulfate colour fades with the rightis the stagebe added).brown how solution should at which starch (this flask iodine is titrated with thiosulfate as the iodine is titrated with colour fades to paleadded). as the yellow solution should be which starch (this is is titrated at is the stage at thiosulfate (this iodine the stage with thiosulfate Figure 3 Upon addition of starch the solution should be added). should which starch solution (this is the stage at which starch solutionUpon addition of starch the blue-black Figure 3 takes on a added). colour solution should be be added). due to 3 Upon addition of starch-the the formation of a starch solution Figure takes on a blue-black colour iodine complex. a blue-black colour due to the formation of a starchsolutionUpon addition of starch the Figuretakes on Upon Figure complex. addition of iodine 3 3formation of a starchdue to the solution takes colour solution takes on a blue-black on a starch the iodine complex. due to the formation of a starchblue-black colour due to the iodine complex. a starch-iodine formation of complex.

Figure 4 As more thiosulfate is added and we near the titration Figure 4 As more thiosulfate is endpoint, the blue-black colour from added 4 As more thiosulfate is Figure and we near the titration the starch-iodine complex fades. endpoint, the blue-black colour from added and we near the titration Figure 4 As more thiosulfate Figure 4 As more thiosulfate is the starch-iodine complex fades. endpoint, the blue-black colour from is added and we near the added and we near the titration the starch-iodine complex fades. titration endpoint, the blueendpoint, the blue-black colour from the starch-iodine complex fades. black colour from the starch-

iodine complex fades.

Figure 5 The endpoint of the titration The endpoint of the Figure 5 is reached when just enough thiosulfate whenthe to react titration The endpoint added Figure 5 is reached is of just with all thereachedpresent and the enough thiosulfate when just react titration Theiodine is added to Figure 5the iodine colourless. the Figureis The endpoint of 5 endpoint of the solutionthiosulfate is added to the with all becomes present and react enough is reached when just titration becomes colourless. just titration is reached when solutionthe iodine present and the with all thiosulfate is added to react enough thiosulfate is added enough solutionthe iodine colourless. the with all becomes present and to react with all the iodine solution becomes colourless.

present and the solution becomes colourless.

8 Fill a burette with sodium thiosulfate solution and titrate each flask with sodium thiosulfate. When the

2 2 2

brown iodine colour fades to yellow (figure 2), add 1mL of starch solution and keep titrating until the blue colour disappears (figures 35). Titrate the blank flasks first, and repeat until concordant results are obtained (titres agreeing to within 0.1 mL). Then titrate each of the alcohol samples. If the three samples of the beverage do not give concordant results, further samples will need to be prepared.

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Result Calculations
The blank titration tells you how much acid dichromate was present at the start. As no alcohol was added the full amount of the dichromate is still present. The blank titrations are carried out so the result can be compared with those of the sample titrations. 1. Determine the average volume of sodium thiosulfate used for your sample from your concordant sample results. 2. Determine the average volume of sodium thiosulfate used for the blank titration from your concordant blank results. 3. Subtract the volume of the sodium thiosulfate solution used for the sample titration from the volume used for the blank titration. This volume of the sodium thiosulfate solution is now used to determine the alcohol concentration. 4. Calculate the number of moles of sodium thiosulfate in this volume. 5. Using the equations, determine the relationship between the moles of sodium thiosulfate and the moles of ethanol. as 6 mol of S2O32- is equivalent to 1 mol of Cr2O72 and 2 mol of Cr2O72- is equivalent to 3 mol of C2H5OH then 1 mol of S2O32- is equivalent to 0.25 mol of C2H5OH 6. Use this ratio to calculate the moles of alcohol in the sample solution. 7. Remember to allow for the dilution factor eg. if the dilution was 1:20 the result needs to be multiplied by 20. 8. Convert the answer in moles per litre to percentage (grams per 100mL) to compare with the figure given on the bottle of the alcoholic beverage tested.