: EXPERIMENT 4.1 Experiment : Study the effect of addition of HCUNaOH on pH to the solutions of (a) acetic acid (W) sodium acetate and (c) a mixture of acetic acid and sodium acetate. 4 _ Requirements : 1-0 M HCl, 1:0 M NaOH, 10M (CH3COOH, 1-0 M CH3COONa, pH meter, buffer = (pH = 4 and 9), distilled water, thermometer, beakers, pipette, burette. (a) Addition of HCI/NaOH to the solutions of acetic acid Fr Theory : Acetic acid is a weak acid, it dissociates to a very small extent. : CH;COOH == CH;COO- + H* When a few drops of HCI solution is added to acetic acid solution, t there will be increase in H* ion ae eeues A TEXTBOOK OF PHYSICAL CHEMISTRY Sem og, eee tee ee Saree reer ees cr Seat oe aa ae eet eis Seca! men (© Rinse the pH electrode with distilled water, Calibrate the pH meter against a butler of trong a. @ Prpare 2 010 M acetic acid solution by measuring out 10-0 mL of the 1-0 M acetic sit ing 200 mk. graduated cylinder. Then add distilled water to get a final volume of 100 mi. Sur ge Solution geaily Wik stirring rod. (@)_Diwie the 0-10 M acetic acd solution into two 50 mL portions. Place the two portions io sao clean dry 100 mL. beakers. @) Note the initial pH of one of these solutions. (© Aad 1-0 mt ofthe HCI stock souion of ont ofthe portions ofthe solution in a beste ta ‘hem and record the pH, (9 Add 1-0 ml of the NaOH stock solution to the second portion of the solution. Mix them ant ‘record the pH. by mixing equimolar solutions of acetic acid ad ss Smee acct, Being a sat is almost comely 88 well a8 CHsCOO” and Na” ions. Let . « Feebly dissociated Thus, the H* ions addea - le hg inte po eet Wy be sca ios presen inte nine, Te— scale 313 present in the mixture ; OH" +CHCOOH —+ CHCOO- + 1,0 ‘Tous, again, there is very lite change in the pH of the mixture SF cxnttotral, be, clear from the above mechanism of buffer action that reserve acidity of Heer of CH CCO cae i die to the presence of CHSCOOH and reserve alkateny ity ot presence of CHsCOO™ ions, eeraee a solution by measuring out 10-0 ml. ofthe 1-0 M acetic ae solution in 100 mi. ’ are tag inder. Add 10-0 mL of te 1-0 M sodium acetate tothe graduated cylinder Tres lilt it with distilled water to get a final volume of 100 mal (Repeat steps (it) 0 (of part (a) with abov We solution, Observations and Calculations ; 5 Room temperature = 1°C ‘Solution Initial pH | pH after addition | pH after addition of1-OmL of |” oft-0mL of r 1.0MHCL 10M NaOH (010M CH,COOH 0-10 M CH;COONa (0-10 M CH;COOH+0-10 M CHsCOONa Precautions : © The temperature control knob ofthe pH meter should be adjusted tothe room temperature. (@ The pH meter shouldbe first calibrated by taking a buffer of known pH. (Gi), Rinse the pH electrode thoroughly with distilled water and gently pat it dry before placing it in 2 solution whose pH is tobe measured. () fier the addition ofthe acid/alkali, the solution should be thoroughly stirred, (Allow at least 15-20 seconds, for the pH reading to stabllizé before recording your measurements (0) When not in use, place pH electrode back into its storage solution, EXPERIMENT 4.2 Experiment : Prepare buffer solutions of sodium acetae-acetc acid of different pH values. ‘Requirements: pH meter, sodium acetate, acetic acid, burete, pipette, thermometer, ble stuns H = 4 and 9), beakers. + Refer Experiment No. 4.1 (c). 0:2 M CHsCOONs (27-22 g of CHjCOONa:3H20 dn) and 0:2 M acetic acid sation nt pote nN Re solutions, buffers of diferent pH values anging from 3:42 to 589 can be prepared. 2 ia4 ‘ATEXTBOOK OF PHYSICAL CHEMISTRY (Som ‘acetate slightly, the buffer with higher and higher pH values are obtained. ‘ua (Git) Butter sotutions with various pH ranges should be prepared according to the Table 4,1 Table 4.1, Acetic aci-sodium ace 50 ing te buffers (18°C), pH range 3.42 105.89 02M Acetic acid (em) | 0.2M Sodium acetate (em pL 95 05 342 90 10 an 80 20 405 70 30 40 60 40 445 30 50. 40 40 60 430 30 70 438 20 80. 53 10 90 357 os 9s 5% EXPERIMENT 4.3 Experiment : Prepare buffer solutlons of ammonium hydroxide-ammonium chloride of diferent values. Requirements: Standard HCI solution, ammonium chloride, ammonium hydroxide, methyl ons indicator, pH-meter, buret, pipet, thermometer, buffer solutions (pH = 4 and 9), beakers, ‘Theory : An alkaline buffer solution has a pH greater than 7. They are commonly prepared {08 ‘weak ase and one of its salt. A frequently used example is a mixture of ammonia solution an amno.lt chloride solution. If these were mixed in equal molar proportions, the solution would have a pt o! 9. ‘Thus, a minture containing equimolar soluons of ammonium hydroxide and its almost completly disd ‘alt, ammonium chloride, constitutes good alkaline buffer. The mixture contains undssociated NH.0 48 well as NH and CI- ions. The buffer action ofthis mixture may now be considered. 1 strong acid is added, the H* ions added are neutralised by the base NH,OH HY + HOH —> —HL0-+ NEY Ifa strong base is added, the OH: ions added are neutralised by NH} ions forming very sch" ‘issocated NHOH. ‘OW + NH; => —_NHOH a | ecbiy disociaed) q In is case idem, reserve acid sd 10 the presente of NI fons and eer all> ‘due othe presence of NH,OH,OO LL pene 315 ‘el of a buffer consisting of a weak base and iss toa, ‘an be calculated by using the Henderson POH = py + tog el [base] PR = 10g Ky of weak base POH + pH = 14 lw (@ Prepare 100 ml of 0-4 M ammonium hydroxide solution. Standaize it against a standard 0-4 M HCI solution using methyl orange as the indicator. From this ammonium hydroxide, prepare 100 mi of exactly 0-2 M ammonium hydroxide by taking required amount from standardized (04M ammonium hydroxide and diluting to 100 mL. with addition of distilled water {@ Prepare 100 ml. of 0-2 M ammonium chloride solution, i) Prepare a series of standard buffer solutions by mixing different volumes of 0:2 M ammonium Ihydroxide and 0-2 M ammonium chloride as given in the folowing observation table | (@) Note the pH value of each solution using pH-meter and also calculate the theoretical value wing Henderson equation (refer example 4,2 Se. 43) Observation : r ‘pK, of ammonium hydroxide = 4.74 Volune f02M_|__Vaune toa] pOH= | pit i4-pH | iin ot) | NHC ol) | pay 2 "8 base) > 7 5 2 7 3 6 4 5 5 4 6° 3 7 2 8 1 ° ‘Calculations : For buffer no. 1. feat, = ps4 | 10H = py oe Te r OH = 474 + log b= 4:74 + (-095) = 3° ‘ PH = 4-378= 10 ‘0,2 POH. = 4.74 + log 2/8 = 9,86 + Refer Experiment No. 41.[A TEXTBOOK OF PHYSICAL CHEMISTRY (Ser) Hong EXPERIMENT 4.4 Experiment : pH metic ttraion of strong acid (HCY) with strong base (NaOH) Requirements : Burette, pipette, beaker, themometer, pH-meter, buffer solutions of known py, 0-1 NN2OH, 0:1 N HCI, distilled water ‘Theory : On addition of alkali to an acid solution, the concentration of H* ions will decrease and hence the pH will increase. In the beginning the pH increases slowly but at the ‘equivalence point, it changes rapidly owing tothe rapid increase in the fraction of H* ions removed by the addition of constant ‘volume of alkali. After the equivalence point, pH decreases slowly. ‘Thus a plot of pH versus volume of alkali added will be obtained as shown in Figure 4.4. Procedure : ( Standarize NaOH and HC! solutions. i) Calibrate the pH meter withthe buffer solutions of known Pi. (ii) Take 20 mL of HC! solution (0-1 N) in a beaker. Measure its PH. (Go) Ada alkali soution (NaOH, 0-1 N) in 0-5 mL ots. Shake well after each addition and measure the pH at each stage. (9) Note the pH till 25-0 ~ 30-0 mL. of NaOH solution has been added. Observations Room temperature = °C ‘Volume of HCI solution taken for ration = 20 ml. equivalence point be ‘Volume of NaOH added (mL) Fig. 44 Pt of pv volume of lil S.No. ‘Volume of 0-1 [NaOH added (mL) L 2 3 4 300 Calculations: A graph is ploted taking pH values on y-axis andthe volume of NeOH ade (1) ‘on the x-axis. The curve obtained is shown in Figure 4.4. From this, ‘note the volume of titrant used ‘the neutralization of 20 ml of 0-1 N HCI i.e, equivalence point.EI ae SCALE 317 Calculation of normality of HC! solution ‘Volume of 0-1 N NaOH used for neutralisation of 20 mL of 0-1 N HCI = V2 mL Applying normality equation NV, = Nao HC] NaOH Nj x 20 = 0.1 x V2 1 Vy == b Vv, => Nig 35 <0 Wh 2ei:209 N 4 Normality of given HCI solution = xz N "Calculation of strength of HCI solution Strength = Normality x equivalent mass ede seca 500 * 365 giltre gilitre, + Strength of given HC! solution + Refer Experiment No. 4.