Chemistry 20L

Study Guide for Cumulative Exam #2

EXAM TIMES & LOCATIONS:

Winter 2013

LECTURE 1 ONLY: LECTURE 2 ONLY:

WEDNESDAY (Mar. 20th) MONDAY (Mar. 18th)

3:00 - 6:00PM in CS76 3:00 - 6:00PM in CS24

Refer to the exam information handout posted on CCLE for the ACTUAL EXAM TIME ASSIGNMENT for the lecture section that you are officially enrolled.

NO EXTRA TIME will be given if you are late to the exam. NO MAKE UP EXAM WILL BE GIVEN. Exam is CLOSED book and CLOSED notes. Exam taken in the wrong lecture section (or incorrect exam session) will be discredited (i.e. zero). You will need to bring a CALCULATOR (SAT APPROVED TYPE) & your UCLA student ID to the exam. Disclaimer Please note that the questions on this study guide do NOT necessary reflect the style of the questions you will actually see on the exam. It is the concepts that you should focus on when working on the following questions. Please keep in mind that a question can be written in many different ways that relates to the same concept(s).
It is your choice to decide whether you want to work through the questions on this study guide.

Complete office hours for the finals week are posted on CCLE by Wednesday (Mar. 13). Exam will cover ALL the experiments and topics/concepts that covered in the course. Note: Besides going through this exam study guide, you should complete the online practice exam before the actual exam (see below). You will receive 2 BONUS points for completing the online practice exam by the deadline for the lecture section that you are officially enrolled in the course. Refer to cumulative exam #2 information handout posted on CCLE for more information on how to access the practice online exam as well as the actual exam time assignment. EXAM FORMAT: Majority of the questions on the exam will be in MULTIPLE CHOICE format. The exam may include other types of questions such as matching type question(s) and/or numerical response type question(s). The online practice exam consists of ALL these types of practice questions. Although the questions on this study guide are not constructed in multiple choice formats, they can easily be converted to multiple choice type questions. You should go through all the lecture materials; writing assignments; online tutorials; technique videos and lab reports when studying for the exam. Focus on the conceptual understanding of various topics. You should also review all the reports including all the experimental procedure. You will need to understand the chemistry rather simply reading the procedure without understanding the concepts behind the various experiments.

(II) Chemical Aqueous Equilibrium and Buffer Chemistry Review the concepts in acid-base equilibrium from your 20B textbook. Focus on the CHEMISTRY rather than the mathematics. (1) Which of the following molecules are acids and which ones of them are bases? HNO3, CH3COOH, NH4Cl, H2CO3, C6H5NH2 (2) Write the chemical reaction with base (OH-) for those molecules that you identified as acids in question #1. Write the formula of the conjugate bases for these molecules. (3) Write the chemical reaction with acid (H+) for those molecules that you identified as bases in question #1. Write the formula of the conjugate acids for these molecules. (4) (a) Explain why the equivalence point pH=7 for a strong acid and strong base titration? (b) Explain why the equivalence point pH >7 for a weak acid and strong base titration? (c) Explain why the equivalence point pH <7 for a weak base and strong acid titration? (You should explain this question by showing the relevant chemical reactions) (5) What volume of 0.250 M NaOH is required to reach the equivalence point with 18.49 mL of 0.200 M H2SO4? (For simplicity, you may assume the 2 proton dissociate completely in H2SO4) (6) What volume of 0.500N NaOH is required to titrate with 100.0ml of 0.120 N of H2SO4 to the equivalence point? (7) Calculate the [H+], pH, [OH-] and pOH in 0.030 M HCl. (8) Suppose you have a 50.00ml of 0.0100 M chloroacetic acid solution, HC2H2O2Cl. Ka=1.410-3. Think about what the predicted pH should be before you even start working on this question. (a) What is the initial pH for this solution? (b) Write down the molecular formula for the conjugate base of chloroacetic acid. (c) What is the equivalence point pH if the chloroacetic acid was titrated with 0.0100M NaOH? What acid-base equilibrium principle did you use when calculating the EQUIVALENCE POINT pH? What major chemical species exist(s) at the equivalence point? (d) Is there any relationship between the strength of the conjugate base for chloroacetic acid and the equivalence point pH that you calculated in part (c)? (9) Which of the following solution pairs can be used as buffers? Explain and write balanced chemical reactions (i.e. the addition of H+ and OH- to the mixture) to support your answer. HOH / KOH; (b) NH4Cl / NH3; (c) K2CO3 / NaHCO3; (d) Na2CO3 / K2CO3 (10) Suppose you have a solution that was prepared by mixing nitric acid (HNO3) with potassium nitrate (KNO3). Explain whether the resulting solution is a buffer. You should approach this problem using the concept of chemical equilibrium constants.

(11) Suppose you have a 100.00ml of 0.01000M methylamine (CH3NH2) solution (Kb=4.410-4). (a) Calculate the pH of this solution. (b) What is equilibrium pH after the addition of 50.00mL of 01000M HCl to methylamine? (c) What is the equilibrium pH after the addition of 70.00mL of 01000M HCl to methylamine? Does the equilibrium pH make physical sense? (d) What is the equivalence point pH for the titration of 0.01000M HCl with methylamine? Does the equivalence point pH make physical sense? (12) Calculate the pH of the solution by mixing 50.00 mL of 0.2000 N NH3 (Kb = 1.810-5) with 10.00 mL of 0.1000 N HCl. (13) Suppose you want to prepare a 1 liter acetate buffer solution at pH=3.95 which contains both 0.10M sodium acetate and 0.15M acetic acid. How much volume do you need for each of these 2 solutions in order to prepare this buffer?? Ka for acetic acid = 1.810-5 (14) Complete question #2 (refer p. 68 in your lab manual) under week 1 of the vinegar experiment. (15) Complete question #3 (refer to p.68 in your lab manual) under week 1 of the vinegar experiment. (16) Consider the following solutions: (i) A solution consists of 0.10 moles of a weak monoprotic acid and 0.20 moles of NaOH. (ii) A solution consists of 0.10 moles of a strong monoprotic acid and 0.20 moles of NaOH. (iii) A solution consists of 0.10 moles of a strong monoprotic acid and 0.10 moles of NaOH. (iv) A solution consists of 0.20 moles of a weak monoprotic acid and 0.20 moles of NaOH. (v) A solution consists of 0.20 moles of a weak base and 0.20 moles of NaOH. (vi) A solution consists of 0.20 moles of a weak base and 0.20 moles of HCl. (vii) A solution consists of 0.20 moles of a weak base and 0.10 moles of HCl. NOTE: You do not need to set up a complete ICE table in order to complete the following questions. All you need is to examine ALL the solutions listed above and determine what chemical species exist(s) when the system reaches equilibrium. From then on, you should be able to answer the following questions. (a) Upon mixing, which one of the above solutions has a pH of 7? Explain. (b) Upon mixing, which one of the above solutions will result in a buffer solution? Explain. (c) Upon mixing, which one of the above solutions will yield a weak base solution but NOT a buffer? Explain. (d) Upon mixing, which one of the above solutions will yield a weak acid solution but NOT a buffer? Explain. (e) Upon mixing, which one of the above solutions will exhibit no chemical reaction among the starting chemical species? Explain. (17) Derive the Henderson-Hasselbalch equation for any buffer solution containing HA / A and an acid -5 dissociation constant that is less than 10 . Review the lecture guide and your 20B textbook for details on acid-base equilibrium as well as buffers chemistry. (18) Define the definitions of equivalent weight for an acid and a base. (19) Calculate the equivalent weight of H3PO4 based on the following reactions: 23(e) H3PO4 + 2OH = HPO4 + 2H2O; (ii) H3PO4 + 3OH = PO4 + 3H2O Experimental Equivalent Weight (grams per equivalent of H+ or OH-) = Weight of sample (Normality of the titrant Volume of the titrant)
-

(II) Error Analysis, Concentration Units and Beers Law (Review from Exam #1 Materials) (20) Calculate the percent error for the following quantities. (a) (20.54 0.02 0.254 0.003) (3.21 0.05) (b) 30.078 0.003 - 20.174 0.001 + 9.813 0.005 (21) Calculate the absolute errors for the quantities in question 20. (22) Describe briefly the meanings of systematic errors and random errors. (23a) Mg(OH)2 is one of the active ingredients in Maalox (an antacid). Suppose you prepared a stock solution by dissolving 0.0558g (weight obtained from digital balance) of Mg(OH)2 in a 50-mL volumetric flask. Calculate the molarity, ppm and w/v % of the Mg(OH)2 stock solution. Your final answers should have the correct units and significant figures. (23b) Calculate the % relative error (for the molarity) in the Mg(OH)2 solution. (Refer to page 31 of the manual for the absolute errors in lab equipment). (23c) Calculate the absolute error (in molarity) for the Mg(OH)2 solution. (23d) Magnesium hydroxide reacts with acid based on the following reaction: Mg(OH)2 + 2H+ = 2H2O + Mg2+ Calculate the normality (N) for the Mg(OH)2 solution in part (a). Show all your reasoning including any conversion factors between molarity and normality. (24) Suppose a student dissolved an unknown sample containing Ni(II) sulfate by using 25.0mL of distilled water and 10.0mL of 0.5M HCl. The solution was then transferred quantitatively to a 100mL volumetric flask. If Beers law analysis was used to determine the concentration of Ni(II) sulfate in the solution, what should be the components for the blank solution? What should be used as standard solutions? (25) Carefully examine the following statement. Is the statement true or false? If the statement is false, explain WHY the statement is false. Different solutions with the same color and identical absorbance values have identical molar absorptivity constants. Review the concepts in solutions concentrations and serial dilution. Know the units of ppm, ppb, w/v%, normality(N), molarity(M) and error analysis (refer to lecture guide #1 for general principle on error analysis ). Your Beers law post-lab report is an excellent reference for Beers law, concentration units, serial dilution and error analysis. At this point, you should be able to derive the expression for inherent error base on the equation you use in data analysis (refer to the Beers law post-lab report; indicators analysis post-lab report and the acetic acid analysis post-lab report). The online tutorials (Beers law & solution concentrations) listed on CCLE report guideline for Beers law assignment may be useful when studying for the exam.

(III) Distillation Phase Diagram and Gas Chromatography (GC) 26. (a) Draw the liquid-vapor phase diagram for binary component system based on the following data. (i) Hexane (b.p. = 68 C) and octane (b.p. = 125 C ) form an ideal solution. (ii) A solution containing 30% hexane has a boiling point of around 97 C. At 97 C, the first drop of the distillate for this mixture has a composition of 60% hexane and 40% octane. (iii) A solution containing 90% hexane has a boiling point of around 70 C. At 70 C, the first drop of the distillate for this mixture has a composition of 98% hexane and 2% octane. Label the axes and the phases in each area. Based on the phase diagram you sketched, indicate the temperature at which a 60% octane solution will begin to boil. What is the composition of the vapor in equilibrium with the solution?
140 T E M P E 120 R A T U 100 R E
O

C 80

60 0 0.2 0.4 0.6 0.8 1.0

MOLE FRACTION OF HEXANE

(b) Sketch the gas chromatogram that would result if the original mixture were separated by gas chromatography on a non-polar column. Note: Both hexane and octane are non-polar. (c) Sketch the gas chromatogram that would result if the distillate from the vapor in equilibrium with the original mixture were separated by gas chromatography on a non-polar column. Review the concepts of intermolecular forces that we discussed in lecture. Focus on how the strength of intermolecular forces relate to boiling point. Refer to study question #2 (page 83 -84 in the manual) assigned for the Distillation/GC pre-lab report for concepts involving intermolecular forces.

(IV) Chemical Kinetics 27. The data below were collected for the following reaction: 2NO2(g) + F2(g) 2NO2F(g) [NO2] (M) 0.100 0.200 0.200 [F2] (M) 0.100 0.100 0.200 Initial Rate (M/s) 0.026 0.051 0.103

Write an expression for the rate law; determine the average rate constant (with correct unit) and the overall order of the reaction. Review the lecture guide, your post-lab report & CHEM 20B textbook on chemical kinetics. You should know how to use kinetics rate data to find out the rate law (like what we did in lecture). Know the relationship between the various integrated rate equation and the order of the chemical species in the kinetics rate law (refer to lecture guide and the post-lab report). Review all the concepts behind the chemical kinetics experiment you did in the lab. There are plenty of questions you can practice from your CHEM 20B general chemistry textbook on chemical kinetics. Focus on the topics/concepts related to the kinetics experiment, integrated rate law and using data to determine experimental rate law.

Answers to Practice Problems

(1) Acid : HNO3, CH3COOH, NH4Cl, H2CO3 Conjugate Bases: NO3 ; CH3COO , NH3, HCO3 (2)
-

Base: C6H5NH2 Conjugate Acids: C6H5NH3

H+ + OH- = H2O; CH3COOH + OH- = CH3COO- + H2O; NH4+ + OH- = NH3 + H2O H2CO3 + OH- = HCO3- + H2O; H+ + OH- = H2O C6H5NH2 + H+ = C6H5NH3+ (a) Final product is H2O and a neutral salt; (b) Final product is a weak base. Hydrolysis of the weak base gives out OH(c) Final product is a weak acid. Hydrolysis of the weak acid gives out H+

(3) (4)

(5) (7) (8)

29.6 mL;
+

(6)

24.0 mL;
-13

[H ] = 0.030; pH= 1.52; [OH-]=3.2X10

+

; pOH= 12.48

(a) [H ] =3.1X10-3M; pH=2.51 (simple Ka dissociation question except you will need to use quadratic equation to solve for pH due to the magnitude of Ka) (b) Conjugate base: [C2H2O2Cl] (c) The major chemical species exists at the equivalence point is C2H2O2Cl . Equivalence point pH is determined by the HYDROLYSIS equilibrium of C2H2O2Cl in water. [OH ] =1.9X10-7M; pH=7.28 (the concept for this part is IDENTICAL to what we did in class for determining the equivalence point pH) (d) Since the Ka for chloroacetic acid has an order of magnitude of around 10-3, the magnitude of Kb for its conjugate base is around 10-11. Therefore, the conjugate base of chloroacetic acid should be very weak. This is the reason why the equivalence point pH is almost neutral (i.e. close to 7).

(9) (10)

Buffers: NH4Cl / NH3 and K2CO3 / NaHCO3 No, the resulting mixture is NOT a buffer since nitric acid is a strong acid (Ka is in the order of 105) so its conjugate base is an extremely weak base (Kb is practically zero). (a) pH = 11.31; (b) This is at the HALF equivalence point; pH = pKa = 14-pKb = 10.64 (c) pH = 10.27 The pH should be lower than the pKa because this is beyond the HALF equivalence point and the solution at this point consists of more conjugate acid (RNH3+) than its conjugate base (RNH2). (d) pH = 6.47 The equivalence pH should be less than 7 due to the formation of the conjugate acid of methylamine. However, methylamine has a Kb value of 4.4010-4, this means the Ka for its conjugate acid is 2.2710-11. Because of such a small Ka value, we expect the equilibrium equivalence point pH to be just below 7 (or very close to neutral!).

(11)

(12) (13) (14) (15)

pH = 10.21 Need approximately 190 ml of sodium acetate and approximately 810 ml of acetic acid. pH = 2.41 (acetic acid sample with no extra water added ); pH= 2.71 (acetic acid sample with water added) No change in equivalence point volume. Equivalence point pH= 9.04 for the titration of acetic acid solution without the extra water. Equivalence point pH = 8.92 for the titration of vinegar solution with the extra water added. You should notice that the equilibrium pH is less basic than the one without the extra water added. (a) solution (iii); (b) solution (vii); (c) solution (iv); (d) solution (vi); (e) solution (v) For this question, you simply need to examine the moles of the starting materials and then write out the chemical reaction like what we did in class to see what final product(s) remain(s) at equilibrium. In other words, you do NOT need to solve for the entire equilibrium using Ka and or Kb. You simply need to know what chemical species exist when the system reaches equilibrium.

(16)

(17) (18)

Refer to your 20B textbook for the origin of the Henderson-Hasselbalch equation. For acid: Equivalent weight = weight of the substance in grams / 1 equivalent of H
+ -

For base: Equivalent weight = weight of the substance in grams / 1 equivalent of OH (19) (20) (21)
+ ; 48.99g H3PO4 / eq. H + 32.66g H3PO4 / eq. H

(a) 3% ; (b) 0.05% (Report to only 1 significant figure) (a) 0.05 ; (b) 0.009 The two topics are discussed on page 22 of your lab manual. 0.0191 M; 1.12X10 ppm; 0.112%
3

(22)
(23a)

(23b) 0.4% (you will get 0.5% if you round off number during each step of the calculation!!) (23c) 0.0001M (actual value is 0.00008M); (23d) 0.0382 N Mg(OH)2
(24) The blank solution should contain 0.5M HCl and distilled water. To be more specific, the ratio of the HCl to water in the blank should be roughly about 1: 9 by volume. Pure and dried Ni(II) sulfate should be used to prepare the standard solution. (25) The statement is FALSE. Molar absorptivity constant varies with chemical species. Different solutions with the same color AND identical absorbance values do not necessary imply identical molar absorptivity constant. Remember absorbance value is a function of molar absorptivity constant; path length and concentration. Identical absorbance values do not always imply identical molar absorptivity constant.

(26) (a) A 60% octane solution will begin to boil at around 90 C. The composition of the vapor in equilibrium with the solution contains about 70% hexane and 30% octane. Note: Your answer may be slightly different depending how you sketch the phase diagram.

(26) (b) Gas chromatogram of original mixture.

injection time (t=0)

hexane Paper direction

octane

(c) Gas chromatogram of first distillate.

(27) Rate = k[NO2][F2];

k (average) =2.6M-1s-1; SECOND order

Solutions to SELECTED Practice Exam Questions

(5) Use Ma Va = Mb Vb; make sure that Ma = 0.400M NOT 0.200M (for molarity, you will need to take into the account of the number of protons in the acid before calculating the equivalence point volume) make sure that Na = 0.120N NOT 0.240N (remember that normality automatically take into account of the 2 protons in sulfuric acid)
-

(6) Use Na Va = Nb Vb;

(8) For part (a), set up the equilibrium table for the hydrolysis of chloroacetic acid (HC2H2O2Cl = H+ + C2H2O2Cl ). This is identical in concept to what we did in lecture to determine the initial pH. For part (c), set up the equilibrium table for the hydrolysis of chloroacetate C2H2O2Cl + HOH = OH + HC2H2O2Cl This is identical in concept to what we did in lecture to determine the equivalence point pH. At the equivalence point, all the chloroacetic acid has converted to chloroacetate. The equilibrium pH will be defined by the hydrolysis equilibrium shown above. (11) First, represent methylamine as RNH2. It makes it easier when setting up the ICE box. (a) Initial pH (Hydrolysis of the weak base) RNH2 I C E 0.01000M -y 0.01000M y + H2O ---= RNH3 -+y +y
+
-

OH

-+y +y

You can calculate the initial pH by using the Kb and the initial concentration of the weak base (similar to what we did in class for the weak acid). Kb = y (0.01000M y)
Use quadratic equation to solve for y = [OH ]. Use that to find pOH and then the pH. Remember, whenever you use Kb, you are actually solving for [OH ]. Therefore, what you get is the pOH (NOT pH). You will need to convert pOH to pH at the end of the calculation.
2

(b) Note: Methylamine (RNH2) is a weak base. It can react with HCl to form a conjugate acid. RNH2 + H+ = RNH3+ (in this case, RNH3+ is the conjugate acid of RNH2) Write out the chemical reaction and then set up the ICE table to determine the pH. (Continue on next page)

11 (c). Now set up the ICE box (in MOLES) that corresponds to the equilibrium that exists at this point. RNH2 I C E 0.01000M* 0.10000L + H+ = RNH3 ----+ 0.01000M* 0.07000L 7.00010-4
+

0.01000M* 0.07000L

-0.01000M* 0.07000L -0.01000M* 0.07000L 3.0010-4 0

This is a BUFFER solution! Use the Henderson-Hasselbalch equation to solve for BUFFER pH TOTAL VOLUME = 100.00mL + 70.00mL = 170.00mL (i.e. initial amount + the total amount of HCl added) Divide the moles of each quantity in the ICE box by the total volume and then put them into the HendersonHasselbalch equation: pH = pKa + log {[RNH2] / [RNH3+]} = (14-pKb) + log {[RNH2] / [RNH3+]} = 10.27 The pH should be lower than the pKa because this is beyond the HALF equivalence point and the solution at this point consists of more conjugate acid (RNH3+) than its conjugate base (RNH2). (d) Calculate the equivalence point volume for the titration first. Note: Methylamine (RNH2) is a weak base. It can react with HCl to form a conjugate acid. RNH2 + H+ = RNH3+ (in this case, RNH3+ is the conjugate acid of RNH2) Write out the chemical reaction and then set up the ICE table to determine the pH. Ma Va = Mb Vb; solve for Va which should be equal to 100.00mL + At the equivalence point, ALL the RNH2 becomes RNH3 . Now set up the ICE box (in MOLES) that corresponds to the equilibrium that exists at the equivalence point. Since the only major species at the equivalence point is the RNH3 , you can set up an ICE box for the hydrolysis of + RNH3 + + RNH3 + H2O = RNH2 + H3O I C E 0.01000M* 0.10000L -y 0.001000 y ----+y +y -+y +y
+

TOTAL VOLUME = 100.00mL + 100.00mL = 200.00mL (i.e. initial amount + the total amount of HCl added) Divide the moles of each quantity in the ICE box by the total volume and then put them into the equilibrium expression: Ka = Kw / Kb = 1.00X10
-14

/ 4.4X10 = { (y / 0.20000L) (y / 0.20000L) } / { (0.001000 y ) / 0.20000L }

-4

Substitute x = y / 0.20000L; where x is now in the unit of M. + 2 Ka = x / (0.005000 M x); solve for x = [H3O ] to find pH.

(12) Set up the ICE box in moles: + NH3 0.2000M* 0.05000L -0.001000 0.009000
+ H = 0.1000M* 0.01000L -0.001000 0 + NH4 -+0.001000 +0.001000

I C E

The ICE box indicates that the final mixture is a BUFFER solution. TOTAL VOLUME = 50.00mL + 10.00mL = 60.00mL (i.e. initial amount + the total amount of HCl added) Divide the moles of each quantity in the ICE box by the total volume and then put them into the buffer equation to find the pH. + pH = pKa + log { [ NH3 ] / [ NH4 ] }; where Ka = Kw / Kb (13) Suppose V1 amount (in Liters) of acetic acid and V2 amount (in Liters) of sodium acetate are required to mixed the buffer. Moles of acetic acid in the final buffer = [HOAc] = 0.15M * V1 Moles of sodium acetate in the final buffer = [NaOAc] = [OAc ] = 0.10M * V2 We also know that the final volume of the buffer is (V1 + V2) = 1L Concentrations of the weak acid and conjugate base in the buffer solution: Divide the moles of each quantity in the ICE box by the total volume (which is 1L) and then put them into the buffer equation: (Equation 2) pH = pKa + log { [ OAc ] / [ HOAc ] } With two equations and two unknowns, you can now solve for V1 & V2 (14) & (15) Questions #14 & 15 are identical to the examples that we did in lecture for a reaction between a weak acid and a strong base. For question #14, hydrolysis of the weak acid determines the initial pH (refer to the lecture note). For question #15, refer to the lecture note on how to determine the equivalence point pH. Note: Water added to the acetic acid solution had no effect on the moles of acidic proton in the solution. This is why the equivalence point volumes between the two different samples of acetic acid remain unchanged. The added water will affect the overall pH since pH depends on the concentration of acidic protons in the solution. The solution with the water added should have a higher pH for question #14 (less acidic) and a lower pH for question #15 (less basic). (16) (a) An equilibrium pH equal to 7 occurs when mixing an equal amount of STRONG ACID with an equal amount of STRONG BASE. (b) One can prepare a buffer solution in three different ways: mix a weak acid with its conjugate base mix an EXCESS amount of weak acid with a LIMITED amount of strong base mix an EXCESS amount of weak base with a LIMITED amount of strong acid

(Equation 1)

You should always remember that a buffer solution MUST consist of both a weak acid and its conjugate base (or a weak base with its conjugate acid) when the system reaches equilibrium. A buffer solution MUST not contain any excess strong acid or excess strong base when the system reaches equilibrium.

16 (c) Since the solution contains ONLY a weak base, this can only happen when you mix an equal amount of weak acid with a strong base. The strong base neutralizes all the weak acid in the solution to form a weak base (or the conjugate base of a weak acid). This is NOT a buffer solution since it contains only a weak base. (d) Since the solution contains ONLY a weak acid, this can only happen when you mix an equal amount of weak base with a strong acid. The strong acid neutralizes all the weak base in the solution to form a weak acid (or the conjugate acid of a weak base). This is NOT a buffer solution since it contains only a weak acid. (e) Any solution that has an acid mix with another acid (or a base with another base) will exhibit no chemical reaction. Note: Refer to your CHEM 20B textbook for common STRONG ACID and STRONG BASE. (17) Suppose that the amount of dissociation is z. X, Y are the INITIAL concentration of the HA and Arespectively. Set up the ICE box in terms of X, Y and z. HA I C E X -z X-z + HOH ------------= H3O+ + ----+z +z AY +z Y+z

X, Y & z have units in molarity(M) Ka = [A-] [H3O+] / [HA] = (Y+z)(z) / (X-z) If Ka is less than or equal to 10-5, we can then assume that z<<Y & z<<X; therefore, Ka (Y)(z) / X Take the log on BOTH SIDE OF THE EQUATION: -log Ka = -log ( (Y)(z) / X) = -log Y log z + log X

This equation can now be simply to (using the definitions of pKa and pH): pKa = -log Y +pH + log X pH = pKa + log Y - log X = pKa + log (Y/X) = pKa + log { [A-] / [HA]} Note: If the Ka becomes too high, the dissociation cannot be neglected. During the process of deriving the buffer equation (refer to the derivation shown above), our assumption is that the dissociation of the weak acid can be ignored. If the dissociation cannot be neglected, the assumption that we made during the derivation will fail and so does the buffer equation. If the Ka of the weak acid in the buffer is too high, one will need to determine the buffer pH using the concept of aqueous equilibrium.