Buffers

J.R.A. Ibale 1INSTITUTE OF CHEMISTRY, COLLEGE OF SCIENCE UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: January 25, 2013 INSTRUCTORS NAME: Maro R. Pea

REFERENCE Petrucci, R.H., et al. General Chemistry, 10th Ed . 2010. APPENDIX ANSWERS TO QUESTIONS 1. What is the pH of a solution containing 0.10 M chloroacetic acid (Ka = 1.4 x 10-3) and 0.15 M sodium chloroacetate? HC2H2ClO2(aq) + H2O(l) C2H2ClO2-(aq) + H3O+(aq) Ka = 1.4 x 10-3 pKa = -log Ka = 2.85 pH = pKa + log = 2.85 + log pH = 3.03 2. What is the composition of 0.10 M CH3COOHNaCH3COO at pH 5.5? If 500 mL of the buffer is to be prepared from 0.50 M CH3COOH and 1.0 M stock NaOH stock solutions, what volumes of the buffer components must be mixed? (a) pH = pKa + log [CH3COO-] = 5.75[CH3COOH] 5.5 = 4.74 + log 5.75 = log (b) The buffer would be 10.65% CH3COOH and 89.35%CH3COO-.

(0.1 M)(500 mL) = 50 mmols [CH3COO-]+[CH3COOH] = 50 mmols 5.75[CH3COOH] +[CH3COOH] = 50 mmols [CH3COOH] = 7.4074 mmols VCH3COOH = [CH3COO-] = 5.75[CH3COOH] = 42.5926 mmols

= 14.81 mL

Table A. ICE Table for the Rxn Between CH3COOH and NaOH CH3COOH(aq) + NaOH(aq) NaCH3COO(aq) + H2O(l) Initial 50 mmol 50 mmol -Change -50 mmol -50 mmol +50 mmol Equilibrium 50 mmol Note: Here it is assumed that the sodium acetate was prepared by reacting 100 mL of 0.5 M CH3COOH and 50 mL 1.0 M NaOH stock soln. Page 1 of 10

[NaCH3COO] = = 0.333 M V[CH3COO-] = = 127.91 mL 3. (a) Calculate the pH of a buffer prepared by mixing 575 mL of 0.50 M formic acid, HCOOH (Ka = 1.7 x 10-4) and 425 ,L sodium formate. (b) What would be the pH if 5.0 mL of 0.15 mL of 0.15 M HCl is added to 95.0 mL of the buffer in (a)? (a) Note: In the Hasselbach-Henderson equation, if the reagents do not have a similar volume it is assumed that they are equimolar. Otherwise, if the volume is unknown and the molarities are provided it is assumed that they are of the same volume. So since they are equimolar, mmols HCOOH = (575 mL)(0.5 M) = 287.5 mmols mmols HCOO- = (425 mL)(0.5 M) = 212.5 mmols pKa = -log Ka = 3.77 pH = pKa + log (b) mmols HCOOH = 3.77 + log = = 3.90 = x mmols = 27.3125 mmols

mmols HCOO- = = = y mmols = 20.1875 mmols + = (5.0 mL)(0.15 M) = 0.75 mmol mmols H pH = 3.77 + log 3.77 + log

pH = 3.67 4. What is the effect on the pH of an ammonium-ammonium chloride buffer if the temperature of the solution is raised? Generally, an increase in temperature decreases the pH of a buffer. So, If the temperature is raised the ammonium-ammonia buffer would become less basic (lower pH). 5. A student needs to prepare a solution whose pH needs to be maintained at 7.00. Given the following Ka values, what would be the best buffer system suited for the solution? Substance Ka pKa HCOOH 1.8 x 10-4 3.74 HClO 3.5 x 10-8 7.46 -7 H2CO3 4.2 x 10 6.38 NH3 5.56 x 10-10 9.25 (CH3)3N 1.35 x 10-10 9.87 Since , out of these substances, only HClO has a pKa (pKa 7.46) nearest to the pH of the solution, pH 7.00, it would also be the best buffer for the solution. 6. What is the pH of 50.0 mL of 0.10 M HCO3- solution? What is the pH of the solution after addition of 0.10 mL of 1.0 M NaOH? H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+(aq) Ka1 = 4.4 x 10-7 HCO3-(aq) + H2O(l) CO32-(aq) + H3O+(aq) Ka2 = 4.7 x 10-11 +] = [H = = 4.548 x 10-9 (a) pH = - log [H+] = 8.34 HCO3-(aq) + H2O(l) CO32-(aq) + H3O+(aq) (50 mL)(0.1 M) = 5 mmols Page 2 of 10 Ka2 = 4.7 x 10-11 (pKa = 10.33)

pH = pKa + log 8.34 = 10.33 + log -1.99 = log [CO32-] = 0.010233[HCO3-] [HCO3-]init = [CO32-]init = [OH-]init = = 0.0988 M = 1.0109 x 10-3 M = 1.996 x 10-3 M

[HCO3-] + [CO32-] = 5 mmols

[HCO3-]+0.010233[HCO3-]=5mmols

[HCO3-] = 4.9494 mmol [CO32-] = 0.010233[HCO3-] = 0.0506 mmol

Table B. Reaction Table of HCO3- and NaOH HCO3-(aq) + OH-(aq) Initial Change Equilibrium 0.0988 -1.996 x 10-3 0.0968 1.996 x 10-3 -1.996 x 10-3 0

CO32-(aq) 1.0109 x 10-3 +1.996 x 10-3 3.0069 x 10-3

H2O(l)

This system is further balanced through the hydrolysis of the carbonate ion. Table C. Hydrolysis Rxn of CO32CO32-(aq) + Initial Change Equilibrium 3.0069 x 10-3 -x 3.0069x10-3 - x H2O(l) HCO3-(aq) 0.0968 +x 0.0968 + x + OH-(aq)
--

+x +x

(b)

Kb = = 2.13 x 10-4 = X = 0.0247 = [OH-]eq pOH = - log [OH-] = 1.61 pH = 14 pOH = 12.39

CALCULATIONS A. Calculation of Volumes of Buffer Reagents Given: 5.0 pH CH3COOH-CH3COO50 mL buffer volume 9.0 pH NH3-NH4+(or 5.0 pOH) 0.2 M acid/base (CH3COOH; NH3) 4.7 pKa & pKb 0.2 M salt solution (Na CH3COO; NH4Cl) 0.1 M buffer concentration 1. Acetic AcidAcetate Buffer (CH3COOH-CH3COO-) pH = pKa + log 5.0 = 4.7 + log 0.26 = log = 0.5495 Page 3 of 10

Since buffer was to have a concentration of 0.1 M to be prepared at 50 mL, (50 mL)(0.1 M) = 5 mmols Which is also, [CH3COOH] + [CH3COO-] [CH3COOH] + 0.5495[CH3COOH] [CH3COOH] = 3.2268 mmols For , = 0.5495 = 1.7732 mmols Volume of each reagent is taken by, V= VCH3COOH = VCH3COO- = = 8.8658 mL 8.87 mL = 16.134 mL 16.1 mL = 5 mmols = 5 mmols

2. Ammonium-Ammonia Buffer (NH3-NH4+) pOH = pKb + log 5.0 = 4.7 + log 0.26 = log = 0.5495 Since buffer was to have a concentration of 0.1 M to be prepared at 50 mL, (50 mL)(0.1 M) = 5 mmols Which is also, [NH3] + [NH4+] = 5 mmols [NH3] + 0.5495[NH3] = 5 mmols [NH3] = 3.2268 mmols For , = 0.5495 = 1.7732 mmols Volume of each reagent is taken by, V= VNH4,+ = VNH3 = = 8.8658 mL 8.87 mL = 16.134 mL 16.1 mL {Note: 9 pH: 5 pOH}

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3. Sodium Biphosphate Buffer (NaH2PO4) pH = pKa + log 4.68 = 7.2 + log -2.52 = log [ = 3.01995 x 10-3[ ] + 3.01995 x 10-3[ = 4.98 mmols = 3.01995 x 10-3[ = 0.015mmols VH2PO4- = VHPO4,2-= = 24.92 mL H2PO4= 7.53 X 10-3 mL HPO42] ] = 5 mmols ]

B. Effect of Strong Acid and Strong Base 1. 0.1 M CH3CHOOH Note: [CH3COOH]init= 0.1 M @ 15 mL1.5 mmols +ACID Since both reagents are acids, no reaction will occur, but both will dissociate within the solution to produce H3O+. Yet, their initial concentrations are now different due to a change in volume. (Note: The initial concentrations of the reagents here are considered to be the same as their concentrations before the addition of the reagents, because the total volume after addition essentially never changed (only 0.67%).) Table 1. ICE Table for Acetic Acid Dissociation in H2O CH3COOH(aq) + H2O(aq) CH3COO-(aq) + H3O+(aq) Initial Change Equilibrium Ka = 0.1 -x 0.1-x -+x +x -+x +x

But since Ka is very small [CH3COOH]eq[CH3COOH]init, and Ka = x= = = Which is also, ( = 1.8 x 10-5 M = [H3O+]CH3COOH M)(15 mL) = 0.020125 mmolCH3COOH H3O+

Since 0.1 mL of 1.0 M HCl(aq) is a strong acid, it dissociates completely to form 1.0 M H3O+, which is also (1.0 M)(0.1 mL) = 0.1 mmolHCl H3O+ So pH is, Page 5 of 10

pH = - log [H3O+] = - log [ = - log [ pH = 2.10 ] ]

+BASE Here, there agents react in a partial neutralization reaction followed by the dissociation of the remaining weak acid from which H3O+ will come mainly from. Also, 0.1 mmol NaOH reacts here since it completely dissociates (Strong Base property), that is, (1.0 M NaOH)(0.1 mL) = 0.1 mmol NaOH Table 2. Rxn Table for the Partial Neutralization Rxn of CH3COOH & NaOH CH3COOH(aq) + NaOH(aq) NaCH3COO(aq) + H2O(l) Initial 1.5 mmols 0.1 mmol -Change -0.1 mmol* -0.1 mmol* +0.1 mmol* Equilibrium 1.4 mmol -0.1 mmol *Note: It is assumed that all of the base reacts with the acid. [CH3COOH]eq = [CH3COO-]eq = = = = 0.0927 M = 6.62 x 10-3 M

Table 3. ICE Table for Dissociation of CH3COOH in H2O CH3COOH(aq) + H2O(aq) CH3COO-(aq) + H3O+(aq) Initial Change Equilibrium Ka =
(

0.0927 -x 0.0927-x
)

6.62 x 10-3 +x
6.62 x 10-3 + x

+x +x

= 1.8 x 10-5

x= pH = - log x = 3.60

=2.52 x 10-4 M H3O+

2. 0.1 M CH3COOH-CH3COO- Buffer CH3COOH(aq) + H2O(aq) CH3COO-(aq) + H3O+(aq) +Acid pH = pKa + log which also relates into moles by, pH = pKa + log = pKa + log Here 0.1 mL of 1.0 M HCl was added or, (0.1 mL)(1.0 M HCl) = 0.1 mmol HCl

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When the acid was added to the buffer system, the equilibrium between CH3COOH and CH3COO- shifts (because the acid reacts with acetate forming acetic acid) and produces the following pH, following the Hasselbach-Henderson equation (Equation 5). (Check: A1 Calculations for ) pH = pKa + log = 4.74 + log pH = 4.44 +Base Similar events occur here except that the equilibrium shifts the opposite way because the base reacted with acetic acid forming acetate. pH = pKa + log = 4.74 + log pH = 4.52 3. 0.1 M NH3 Note: pH in this part of the experinet was obtained indirectly through pOH determination. +ACID Here, there agents react in a partial neutralization reaction followed by the dissociation of the remaining weak base from which OH- will come mainly from. Also, 0.1 mmol HCl reacts here since it completely dissociates (Strong Acid property), that is, (1.0 M HCl)(0.1 mL) = 0.1 mmol HCl Table 4. Rxn Table for the Partial Neutralization Rxn of CH3COOH & NaOH NH3(aq) + Initial HCl(aq) NH4+(aq) + Cl-(aq) 1.5 0.1 --mmols mmol -0.1 -0.1 +0.1 Change -mmol* mmol* mmol* 1.4 0.1 0.1 Equilibrium -mmol mmol mmol *Note: It is assumed that all of the acid reacts with the acid. Here, Cl- is free ion so its presence isnt further deliberated. [NH3]eq = [NH4+]eq = = = = 0.0927 M = 6.62 x 10-3 M

Table 5. ICE Table for Dissociation of CH3COOH in H2O NH3(aq) + H2O NH4+(aq) + OH-(aq) Initial Change Equilibrium Kb =
( )

0.0927 -x 0.0927-x
( )

6.62 x 10-3 +x
6.62 x 10-3 + x

+x +x

= 1.8 x 10-5

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+Base Since both reagents are bases, no reaction will occur, but both will dissociate within the solution to produce OH-. (Note: The initial concentrations here are considered to be the same as their concentrations before the addition of the reagents, because the total volume after addition essentially never changed (only 0.67%).) Table 6. ICE Table for Acetic Acid Dissociation in H2O NH3(aq) + H2O(aq) NH4+(aq) + OH-(aq) Initial Change Equilibrium Kb = Kb = x= = = Which is also, (
[ ]

x= =2.52 x 10-4 M OHpOH = - log x = 3.60 pH = 14 pOH = 10.40

0.1 -x 0.1-x

-+x +x

-+x +x

But since Kb is very small [NH3]eq[NH3]init, and = 1.8 x 10-5

M = [OH-]NH3 M)(15 mL) = 0.020125 mmolCH3COOH H3O+

Since 0.1 mL of 1.0 M NaOH(aq) is a strong acid, it dissociates completely to form 1.0 M OH-, which is also (1.0 M)(0.1 mL) = 0.1 mmolHCl OHSo pH is, pOH = - log [OH-] = - log [ ] = - log [ pOH = 2.10 pH = 14 pOH = 11.9 4. 0.1 M NH3-NH4+ Buffer NH3(aq) + H2O(aq) NH4(aq) + OH-(aq) +Acid pH = pKa + log Here 0.1 mL of 1.0 M HCl was added or, (0.1 mL)(1.0 M HCl) = 0.1 mmol HCl When the acid was added to the buffer system, the equilibrium between NH3 and NH4+ shifts (because the acid reacts with ammonia forming ammonium and hydroxide ions) and produces the following pH, following the Hasselbach-Henderson equation. (Check: A2 Calculations for mol NH3 and NH4+.) Page 8 of 10 ]

pOH = pKb + log = 4.74 + log pOH = 4.52 pH = 14 pOH = 9.48

+Base Similar events occur here except that the equilibrium shifts the opposite way because the base reacted with the ammonium ion forming ammonia and water. pOH = pKb + log = 4.74 + log pOH = 4.44 pH = 14 pOH = 9.56 5. 0.1 M NAH2PO4 Note: This buffer system uses the properties of ampholytes to induce a buffer effect due to their ability to act both as an acid and as a base at their intermediate forms, i.e. in this case H2PO4- and HPO2-. (Note: See A3 for calculations of the initial moles of H2PO4- and HPO42-.) +Acid Since an acid was added to the buffer, the equilibrium of the system compensates the change by forming more H2PO4- each time HPO42- reacts with the acid. Table 7. ICE Table for the Formation of H2PO4- from HPO42HPO42-(aq) + H3O+(aq) H2PO4-(aq) + H2O(l) Initial 3.0109 x 10-4 Change -3.0109 x 10-4 Equilibrium 6.6225 x 10-3 -3.0109 x 10-4 6.3214 x 10-3 0.0997 -3.0109 x 10-4 0.1

But in order to complete the equilibrium process, the reaction wherein H2PO4- forms comes back to form HPO42-. Table 8. ICE Table for the Rxn Dissociation of H2PO4- in H2O H2PO4-(aq) + H2O(l) HPO42-(aq) + H3O+(aq) Initial Change Equilibrium 0.1 -x 0.1 - x 0 +x +x 6.3214 x 10-3 +x 6.3214 x 10-3+x

Ka = x = 9.9796 x 10-7 [H3O+] = 6.3214x10-3+x = 6.32243 x 10-3 M pH = -log [H3O+] = 2.20

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+Base Since a base was added to the buffer, the equilibrium of the system compensates the change by forming more HPO42- each time H2PO42- reacts with the base. Table . ICE Table for the Rxn H2PO4- and OHH2PO4-(aq) + OH-(l) Initial Change Equilibrium 0.0997 -6.6225 x 10-3 0.09308 6.6225 x 10-3 -6.6225 x 10-3 0 HPO42-(aq) 3.0109 x 10-4 +6.6225 x 10-3 6.9236 x 10-3 + H2O(l)

But in order to complete the equilibrium process, the reaction wherein HPO42- forms comes back to resupply the buffer with OH-. Table 9. ICE Table for the Hydrolysis of HPO42HPO42-(aq) + H2O(l) Initial Change Equilibrium 6.9236 x 10-3 -x 6.9236 x 10-3-x H2PO4-(aq) + OH-(aq) 0.09308 +x 0.09308 + x

+x +x

Ka = x = 1.117894 x 10-8 = [OH-] pOH = -log [H3O+] = 7.93 pH = 14 pOH = 6.07 C. %error Determination For all the data, computed the %error was obtained using the following equation, %error = | | The following data was obtained, Table 10. %error of Data in Part B Solution A 0.1 M CH3COOH as is B A 0.1 M CH3COOH- CH3COO- as is B A 0.1 M NH3 as is B A 0.1 M NH3- NH4+ as is B A 0.1 M NaH2PO4 as is B %error 10.95% 4.88% 8.90% 9.23% 1.00% 19.91% 6.15% 9.25% 8.15% 7.91% 0.10% 4.81% 41.82% 2.78% 4.78%

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