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Lecture Notes Darin J. Ulness Department of Chemistry Concordia College, Moorhead MN Spring 2007

CONTENTS

1 Calculus in a Nutshell Rates of Change . . . . . Slope . . . . . . . . . . . . The Anti-Derivative . . . Group Work . . . . . . . . Homework . . . . . . . . .

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7 7 8 9 9 9 11 11 12 13 14 14 15 15 18 18 19 19 21 21 23 23 24 25 25 26 27 28 28

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2 Diﬀerential Rate Laws The Reaction Rate . . . . . . . . . . . Rate Laws . . . . . . . . . . . . . . . . Elementary Reactions and Molecularity Group Work . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . .

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3 Determination of Rate Laws Diﬀerential methods based on the rate law . . . . . . Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 4 Integrated Rate Laws Linearizing the integrated rate laws . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 5 The Arrhenious Equation Temperature Dependence of the Rate Constant Application of the Arrhenious Equation . . . . . Catalysts . . . . . . . . . . . . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . .

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**6 Kinetics and Equilibrium Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . .
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CONTENTS

7 Equilibrium and the Equilibrium Constant The Equilibrium Constant . . . . . . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 8 ICE Charts Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 9 The Reaction Quotient ciple The Reaction Quotient . . LeChatelier’s Principle . . Group Work . . . . . . . . Homework . . . . . . . . . 10 Review for Exam 1 11 Acids and Bases Brønstad Acids and Bases Conjugate Acid-Base Pairs Group Work . . . . . . . . Homework . . . . . . . . . 12 Water and pH The pH Scale . . The pH of Strong Group Work . . . Homework . . . . and LeChatelier’s Prin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

29 29 31 31 33 35 35

37 37 38 39 40 41 43 43 43 44 45 47 48 48 49 49 51 54 54 55 55 57 58 59 59

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13 Acid and Base Equilibria Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 14 Reactions with Weak Acids and Weak Bases Reaction Between a Monoprotic Weak Acid and a Strong Base . . . . . . . . . . . . . . . . . . . . Reaction Between a Polyprotic Weak Acid and a Strong Base . . . . . . . . . . . . . . . . . . . . . . . . Reaction Between a Weak Acid and a Weak Base . . Work Group . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . .

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CONTENTS

. . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 17 Titrations Part I Titration of a Strong Acid with a Strong Base Titration of a Weak Acid with a Strong Base Group Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 71 73 75 75 77 79 79 81 82 83 85 and Hess’ . . . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . 68 Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . Group Work . . . . . . . . . . . Enthalpy. Homework . . . . . . . . . . . . . . .15 The Common Ion Eﬀect and Buﬀers Buﬀer Solutions . . . . . . . . . . . . . . . . . . . . . . . . . 23 The Second and Third Laws Calculating Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . Group Work . . Group Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . 20 Review for Exam 2 21 Review of the First Law. . . . . . . . . . . . . . . . 61 62 64 65 16 More on Buﬀers: The Henderson-Hasselbalch Equation 67 Group Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 Titrations Part II Group Work . . . . . . 19 Solubility of Weak Electrolytes Group Work . . 22 Entropy Microstates and Conﬁgurations . . . . . . . . . . . . . . . . . . Enthalpy . . . . . . . . Homework . . . . . . . . . . . Law The First Law of Thermodynamics . . . . . . . . . . . . . . . . . . 87 87 88 90 91 91 93 93 94 94 95 96 96 97 3 . . . . . . . . . . . . . . Group Work . . . . . . . . . . . . CONTENTS . . . . . . . . Homework . . . . . . . . Hess’ Law . . . . .

104 Group Work . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 123 123 124 126 126 127 33 Intermolecular Forces 129 Polarizability and Induced Dipoles . . . . Homework . . . . . . . . . . . . . . . . . . . . . 133 4 CONTENTS . . . . . . . . . 110 28 Oxidation—Reduction Reactions II 111 Group Work . Group Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Gibbs Free Energy . . . . .24 Gibbs Free Energy The Second Law . . . . . . . . . . . . . Group Work . . 129 Intermolecular Forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130 Group Work . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Standard Cell potentials Group Work . . . . . . . . . . . . . . . . . . 118 Homework . . . . . . . . . . . . . . 111 Homework . . . . . . . . 106 26 Review of Concepts Surrounding Gibbs Free Energy 107 27 Oxidation—Reduction Reactions I 109 Balancing redox reactions . . . . . . . . . . . . . . . . 110 Group Work . . . . . . . 111 29 Electrochemical Cells Cell diagrams . . . . . . . . . . . . . . . . . . 113 114 114 115 115 30 The Nernst Equation 117 Group Work . . . . . 119 31 Review for Exam 3 32 Review of Molecular Geometry Charge Distribution in Covalent Compounds VSEPR Model . 99 99 100 101 102 25 Gibbs Free Energy and Equilibrium 103 ° The diﬀerence between 4rxn G and 4rxn G . . . . . . . . . . . . . . . . . . . . . . . . . . . Molecular Dipole Moments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137 35 Phase Diagrams 139 Group Work . . . Homework . . . . . . . . Group Work . . . . . . . . . . . . Homework . Raoult’s Law . . . . . . . . . Liquid-gas solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 Properties of Solutions Henry’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140 Homework . . . . . . . . . . . . . . . . . . . . . . . . Colligative properties . . . 137 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Homework . . . . . . Liquid-liquid solutions . 140 36 Homogeneous Solutions Liquid-solid solutions . . . . . . . . . . . . . 133 34 Hydrogen Bonding and Water . . . . . . . . . . . . Homework . . . . . Water 135 . . Group Work . . . . . . . . . . . . . . . . . 141 141 142 142 143 143 145 145 146 147 148 149 151 CONTENTS 5 . . . . . . . . . . . . 38 Review for Final Exam . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137 . . . . . . . Group Work . .

Material for Exam I 6 CONTENTS .

The concept of a derivative is one of two central concepts in calculus. We are measuring a rate of change of the reaction. We could consider two times and compare the function at each of these times.1 CALCULUS IN A NUTSHELL It is so much easier to talk about chemical kinetics if we have just a few ideas from calculus. Mathematically the rate of change is called a derivative. We might be watching a reactant disappear as time goes on or we might be watching a reactant appear. Rates of Change When considering chemical kinetics we will be interested in how fast a reaction proceeds. We are interested in how it changes with time. Experimentally this means we are in some way monitoring how the reaction is changing in time. 4t CALCULUS IN A NUTSHELL 7 . The rate of change might then be given by4t 4f . 4f = f (t2 ) − f (t1 ). The following is all the calculus we need to know. Let’s say we have some function that changes with time: f (t).

Slope If we graph the function f then the derivative has a very nice graphical interpretation. Obviously if 4t is big then this might not be the case. If dt is suﬃciently small then df dt is a good measure of the instantaneous rate of change. Unfortunately this only works if the rate of change is constant during 4t. In calculus this is called the derivative of the function f with respect to t. The derivative at any time t is equal to the slope of the function at t. One of the central ideas of calculus is to consider the limit when 4t gets inﬁnitesimally small. We then write dt. 8 CALCULUS IN A NUTSHELL .where 4t = t2 − t1 . Since the derivative is an instantaneous rate of change it holds for any function not just those that have a constant rate of change.

The integral is the answer to the question what function has this derivative? Group Work 1. The other is the anti-derivative. 2. which is more commonly called the integral. Use a plot to show that 4f df = dt 4t only for a straight line. 14.The Anti-Derivative As mentioned above. If a function is decreasing with time is it’s derivative positive or negative. the derivative is one of two fundamental concepts in calculus. If y = mx + b for a straight line.1 CALCULUS IN A NUTSHELL 9 . what is dy ? dx Homework Reading: Evaluation book. If a derivative is always zero what must be true about its anti-derivative? 3. 4.

10 CALCULUS IN A NUTSHELL .

one can easily adjust the derivative of the concentration with respect to time to give a reaction rate. v. C or D with respect to time: d[I] . But. B. Therefore A and B do not disappear at the same rate if a 6= b and C and D do not appear at the same rate if c 6= d. that is consistent regardless of which reactant or product is monitored. We can watch either A or B disappear or we can watch either C or D appear. dt where [I] is the concentration of A. If we inspect the stoichiometry of the above reaction we see that a moles of A react with b moles of B to make c moles of C and d moles of D. C or D. ν I dt (2.2) 11 . The rate (or velocity) of a reaction is v= DIFFERENTIAL RATE LAWS 1 d[I] .2 DIFFERENTIAL RATE LAWS The Reaction Rate Consider the reaction aA + bB → cC + dD. That is. since the stoichiometry is ﬁxed for a given reaction. B. we can monitor the derivative of the concentration of A.1) We can monitor the rate of this reaction in a number of ways. (2.

usually integers and k is the rate constant for the reaction. 12 DIFFERENTIAL RATE LAWS . Thus for the reaction given above v= 1 d[B] 1 d[C] 1 d[D] 1 d[A] = = = −a dt −b dt c dt d dt (2. (2. As a result. That is to ﬁnd the rate law for the reaction.5) The nA and nB powers on the concentrations are called orders of the reaction.4) where nA and nB are constants. Again considering the reaction aA + bB → cC + dD.where ν I is the stoichiometric factor with the understanding that it is negative for reactants and positive for products. Kinetics is very much an empirical science that depends much more heavily on experimental results than on a strong theoretical foundation. A diﬀerential rate law for this reaction is then 1 d[A] = [A]nA [B]nB −a dt (2. rate laws must be experimentally determined rather than theoretically predicted. the rate laws of this type would be v = k [A]nA [B]nB .3) Rate Laws One of the primary goals of chemical kinetics is to determine how the rate of a reaction goes. One very important and very common class of rate laws are ones in which the rate depends on the concentration of reactants present.

Trimolecular A + A + A → Product v = k[A]3 Trimolecular A + A + B → Product v = k[A]2 [B] Trimolecular A + B + C → Product v = k[A][B][C] Conversely. and of overall order nA + nB .7) be the overall reaction. It is very important to note that nA and nB generally do not have any relation to the stoichiometric factors a and b. Elementary Reactions and Molecularity In general an overall reaction is made up of so called elementary reactions Reactant Reactant → → Product overall rxn (2. of order nB in B. DIFFERENTIAL RATE LAWS 13 .Thus one would say this reaction is of order nA in A.6) Intermediates → Product Note that we shall use an equal sign when talking about the overall reaction and arrows when talking about the elementary reactions Example Let 2A + 2B → C + D (2. One possible set of elementary steps could be elementary rxn A + A → A0 A0 → A00 A00 + 2B → C + D molecularity Bimolecular . Unimolecular Trimolecular The rate laws for elementary reactions can be determined from the stoichiometry molecularity elementary rxn rate law Unimolecular A → Product v = k[A] Bimolecular A + A → Product v = k[A]2 Bimolecular A + B → Product v = k[A][B] . rate laws for overall reactions can not be determined by stoichiometry.

2 Problems: Evaluation book Chapter 14: 3. 27. 11. Homework Reading: Evaluation book. write a diﬀerential rate law for it. 63. 12. 9. Group Work 1. 24. 2H2 + O2 → 2H2 O 2. 14. The rate determining step is the one in the series of elementary reactions that has the lowest rate constant k. 51. 28. 26. each time monitoring a diﬀerent reactant or product.One of the reasons why one can not write a rate law directly from the stoichiometry of an overall reaction has to do with the idea of the rate determining step. Write the rate for the following reaction three times. 64 14 DIFFERENTIAL RATE LAWS . If the above reaction is elementary. 5.

3 DETERMINATION OF RATE LAWS Concentrations [I] are measured not rates. • For medium reactions (min) either a continuous monitoring technique or a stopping technique can be used — A stopping technique used rapid cooling or destruction of the catalysts to stop a reaction at a given point. • Very fast (sec/subsec) reactions cause problems because the reaction goes faster than one can mix the reactants. To obtain the rate from the concentration we must examine how the concentration changes with time 1 d[I] ν I dt That is we must measure [I] as a function of time and ﬁnd the rate of change of this concentration curve. Consequently no one experimental technique can be used. • For slow reactions (hrs/days) almost any technique for measuring the concentration can be used. Diﬀerential methods based on the rate law Methods based directly on the rate law rely on the determination of the time derivative of the concentration. Method of initial velocities • for v = k[A]x [B]y rate laws. The rates of chemical reactions vary enormously from subseconds to years. DETERMINATION OF RATE LAWS 15 . 1.

1 M = 0.00050 M/min 10 min (3. Method of isolation • for v = k[A]x [B]y rate laws • repeat for the other reactants Example: Method of Initial Rates Consider the reaction aA + bB → cC and the following experimental data Run I II II [A]0 0. A so v ≈ kax [B]y (3.1 M 0.05 × 0.00025 M/min 20 min 0.2 M [B]0 0.1 M = 0.00100 M/min 10 min Now.3) 0. vIII = (3.2 M = 0.• initially v0 = kax by where a and b are the initial concentrations of A and B respectively • taking the log of both sides gives ln v0 = ln[kax by ] = ln k + x ln a + y ln b • a and b can be varied independently so both x and y can be determined.1 M • ﬂood with. • usually the experiment is run so the order can be easily determined by simple inspection.2 M 0.4) 16 DETERMINATION OF RATE LAWS . • problems (a) if the concentration drops very sharply (b) if there is an induction period 2. say.1 M 0.1 M 0.05 × 0.2) Likewise from runs II and III vII = and (3. by comparison we can obtain the order.1) [A]95% 20 min 10 min 10 min The data from run I gives an initial rate of vI = 0.05 × 0.

Thus doubling the concentration of A quadruples the rate. Example: Method of Isolation Again consider the reaction aA + bB → cC and the following experimental data. order I 1. DETERMINATION OF RATE LAWS 17 (3.6) .01 1. Run [A]0 [B]0 obs. So ﬁnally we can write the rate law as v = k [A]2 [B]. Thus doubling the concentration of B doubles the rate. They are equal to the stoichiometric factors only for elementary reactions.5) Notice the orders have nothing to do with the stoichiometric factors. Therefore the order dependence on [B] must be one. Therefore the overall rate law is v = k [A]2 [B]. (3.01 1 II 0. Comparing runs I and III we see the rate has doubled.00 2 From run I we see that the reaction depends on [B] to the ﬁrst power From run II we see that the reaction depends on [A] to the second power.00 0. Therefore the order dependence on [A] must be two.Comparing runs I and II we see the rate has doubled.

54. 55.1 0.3 Problems: Evaluation book Chapter 14: 14. 48. 49.1 0. Consider the reaction aA + bB + cC → dD and the following data Run I II III IV [A]0 0. Explain in your own words the strategy of the method of isolation.1 M 0.2 0. Consider the reaction aA + bB → cC and the data Run I II II [A]0 0.1 [C]0 0.Group Work 1.090 M 0.1 [A]95% 100 sec 50 sec 100 sec 100 sec what is the overall rate law? 3.1 0.1 0.095 M 0.1 0.2 M 0. 53.1 M 0. Sometimes the initial rate data is presented slightly differently.180 M What is the overall rate law? 2.1 M 0. 18.1 0.1 0.2 [B]0 0.2 0. Homework Reading: Evaluation book. 14.1 M [A]10 min 0.2 M [B]0 0. 56 18 DETERMINATION OF RATE LAWS .

ν i is a negative number). For example n = 3/2 is a three-halves order rate law.1) INTEGRATED RATE LAWS 19 . Linearizing the integrated rate laws We see from the table above that the integrated rate law for ﬁrst order behavior is [I] = [I0 ]eν i kt . b) The order need not be an integer.b.4 INTEGRATED RATE LAWS The previous lecture dealt with diﬀerential rate laws look directly at the rate law which is a diﬀerential equation. type 1st order 2nd order nth orderb) enyzme a) 1 νi 1 νi 1 νi 1 νi rate lawa) d[I] dt d[I] dt d[I] dt d[I] dt integrated rate lawa) [I] = [I0 ]eν i kt 1 = [I10 ] − ν i kt [I] 1 = [I0 ]1 − (n − 1)ν i kt n−1 [I]n−1 [I0 ] km ln [I] + ([I0 ] − [I]) = −ν i kt = k[I] = k[I]2 = k[I]n k[I] = km +[I] [I] is the concentration of one of the reactants in an elementary reaction and ν i is the stoichiometric factor for [I] (n. which is of the form of an exponential. (4. The diﬀerential equation is not solved.. The diﬀerential equations (rate law) and their solutions (integrated rate law) are simply listed here for a few rate laws. We now solve the diﬀerential equations to yield what are called the integrated rate law.

Sometimes.2) ¡ ν i kt ¢ ln[I] = ln[I0 ] + ln e ln[I] = ν i kt + ln[I0 ]. kobs .With a computer and a program like Microsoft Excel it is easy to work with the data as is.5) INTEGRATED RATE LAWS . ﬁrst order reactions will appear as straight lines with a slope equal to ν i k. ln[I] = −kobs t + ln[I0 ] and second order reactions go as 1 1 = kobs t + [I] [I0 ] 20 (4. For a ﬁrst order reaction this is done by taking the natural log of the integrated rate law ¡ ¢ ln[I] = ln [I0 ]eν i kt (4. Thus overall reactions that appear to be ﬁrst order follow the linearized integrated rate law. The second and higher order integrated rate laws given in the table about are already in linearized form. however. by plotting the natural log of experimental data versus time. |{z} | {z } |{z} y mx b So. it is convenient to cast the data into linear form. If a reaction is described by a second order rate law then when one over the data is plotted one gets a straight line with slope −ν i k: 1 1 = −ν i kt + . Instead one uses an observed rate constant.4) (4. (4.3) | {z } [I0 ] [I] |{z} |{z} mx y b The table lists the integrated rate laws for elementary reactions. Over all reactions also follow these rate laws but now one can not express the slopes of the linearized equations as a product of the rate constant and the stoichiometric factor.

20. 2. “m”. dt From what we learned in the ﬁrst lecture.Group Work 1. We have talked about ﬁrst and second order reactions. If we consider a zeroth order rate law. what is the most general type of function that has a constant slope for all time t? (b) Given that [I] must equal [I]0 (a constant. “x” and “b” in the linearized nth order integrated rate law. 62 INTEGRATED RATE LAWS 21 . we can solve this equation. 58. equal to the initial concentration) at t = 0 Homework Reading: Evaluation book. 16.4. 59. The equation is asking us to ﬁnd the function [I] that has a constant derivative that is equal to ν i k. Identify “y”. 61.5 Problems: Evaluation book Chapter 14: 10. 14. 14. (a) Given the slope interpretation of the derivative. we must solve the diﬀerential equation 1 d[I] = k[I]0 = k ν i dt d[I] = ν i k.

22 INTEGRATED RATE LAWS .

That is. Notice that if one takes the natural log of the Arrhenious equation one has ln k = ln A − Ea . RT (5.5 THE ARRHENIOUS EQUATION Temperature Dependence of the Rate Constant We have learned that kinetics is an empirical science.2) 1 If ln k is plotted versus T we get a straight line whose slope is Ea and intercept is ln A. the rate constant gets bigger with increasing temperature. In other words. THE ARRHENIOUS EQUATION 23 . R So one needs to know the rate constant at least two temperatures to determine the Arrhenious parameters.1) where Ea is the Arrhenious activation energy and A is a constant called the frequency factor. One experimental observations is that the rate of a reaction generally increases as the temperature increases. An empirical rate constant that often captures the correct temperature dependence was proposed by Arrhenious: k = Ae− RT Ea (5. it is based more on experiment than on theory.

24 THE ARRHENIOUS EQUATION . So Ae− 400R = 1. What is the Arrhenious activation energy for this reaction? The reaction goes 1. Taking the natural log of both sides gives − Solving for Ea gives Ea Ea − = ln 1.5k300 .5 times faster at 400 K than at 300 K.5 Ea 300R 400R ln 1.47. How much faster will the reaction go at 298 K than at 273 K? We want to ﬁnd the ratio k298 .50 kJ/mol for some reaction. Example 1: A reaction is found to go 1.47 times faster at 298 K than at 273 K.Application of the Arrhenious Equation The best way to get a feel for the Arrhenious equation is to work a few examples.5e− 300R .5 − .5 ¢ Ea = ¡ 1 1 − 400R 300R Ea = 4045 J/mol Example 2: The Arrhenious activation energy is 50.5Ae− 300R Ea Ea e− 400R = 1.5 300R 400R µ ¶ 1 1 − = ln 1.5 times faster means k400 = 1. 1 1 k298 Ae− 298R 50500( 273R − 298R ) = 50500 = e k273 Ae− 273R = 6. So the reaction goes 6. k273 50500 Ea Ea Ea Ea = ln 1. 400R 300R Thus.

Should you heat the reactions or cool the reactions if you want reaction I to go to completion before reaction II? THE ARRHENIOUS EQUATION 25 .Catalysts The Arrhenious activation energy creates a barrier for reactions to proceed. What is the Arrhenious activation energy? 2. One can add a catalysts. A catalyst is a species that participates in the reaction but is not consumed by the reaction. Reactants + Catylist → Products + Catylist (5. We have learned that one way to speed up a reaction is to heat it. A certain reaction goes twice as fast at 1000 K than at 300 K. There is an additional method for lowering the activation energy barrier. Reaction I has a large Arrhenious activation energy and reaction II has a small one. The higher the energy barrier the slower the reaction will go. Both reaction I and reaction II take the same amount of time to reach completion at 298 K. How much faster will the reaction go at 300 K than at 100 K? 3.3) Group Work 1. A certain reaction has an activation energy of 34 kJ/mol. Sometimes heating is not desirable.

7.Homework Reading: Evaluation book. 37. 14.8 Problems: Evaluation book Chapter 14: 131. 33. 74. 14. 39. 68. 41. 75 26 THE ARRHENIOUS EQUATION . 71.. 70. 69.

(6. kr kf r cC + dD → aA + bB.2) (6.4) vf = kf [A]nA [B]nB . vf = vr .5) Equilibrium occurs when the reaction rate in both the forward and reverse directions are equal. aA + aB cC + dD.6 KINETICS AND EQUILIBRIUM Our next topic will be chemical equilibrium. We can understand equilibrium from the standpoint of kinetics by not only considering the forward reaction. There is a relation between kinetics and equilibrium. aA + aB → cC + dD k kf (6.6) (6. These can be written as one reaction with a double arrow. while the rate of the backwards reaction depends on the concentration of products vr = kr [C]nC [D]nD .3) The forward reaction rate depends on the concentration of reactants.1) but also the reverse reaction. however. do not go to completion but reach an equilibrium with a certain amount of reactants still left over. (6. Last semester and up to this point we have been talking about reactions that go all the way to completion. Most reactions. (6. or kf [A]nA [B]nB = kr [C]nC [D]nD [C]nC [D]nD kf = =K kr [A]nA [B]nB KINETICS AND EQUILIBRIUM (6.7) 27 .

Homework Problems: Evaluation book Chapter 14: 78. 81. Does the ratio of rate constants tell us how fast the reaction reaches equilibrium. 80. Hint: consider the units. 82. 84 28 KINETICS AND EQUILIBRIUM .Group Work 1.

EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT 29 . unlike kinetics. the equilibrium constant is deﬁned as K= [C]c [D]d [A]a [B]b .7 EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT Last lecture we began to consider the fact that usually reactions do not go all the way to completion. For a given reaction. Notice here. aA + bB cC + dD. The topic of equilibrium is of essential importance to general chemistry and will be discussed for nearly the rest of the semester. they reach an equilibrium. The ﬁrst topic in equilibrium we will discuss is the equilibrium constant The Equilibrium Constant We already sort of saw the equilibrium constant last time. The equilibrium constant tells us how much of each of the reactants and products are present after the reaction reaches equilibrium. but rather. we can rely on the stoichiometry of the reaction to give us the proper K values.

Here partial pressures are used in place of concentrations. Sometimes concentrations are not the most convenient value to use for the equilibrium constant. Here water is the product and the solvent.Because of this. Product favored reactions are those in which there are more products around than reactants at equilibrium. The concentration of water is not used. In these cases K= [C]c [A]a [B]b . Here [C]c [D]d . Thus K > 1 for product favored reactions. One also does this when pure substances are used as reactants or produces as products. K= [A]a 30 EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT . KP = c d PC PD . a b PA PB Another case where one does not use concentration is when referring to the solvent. Reactant favored reactions are those in which there are more reactants around than products at equilibrium. K provides a criteria for labeling a reaction as product favored or reactant favored. Consider the reaction aA + bB cC + H2 O that takes place in water. One example are gas phase reactions. Thus K < 1 for reactant favored reactions. Consider aA(aq) + bB(s) cC(aq) + dD(aq) .

5. 8. 16.2.Group Work 1.1.3 Problems: Chapter 16: 1. 3. Write the equilibrium constant for the following reactions (a) H2 CO3(aq) + H2 O HCO− + H3 O+ 3(aq) (aq) (b) (c) N2(g) + 3 H2(g) 2 NH3(g) O2(g) + 2 H2(g) 2 H2 O(l) Homework Reading: Kotz and Treichel. 7. 10. 11 EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT 31 . 16. 16. 9.

32 EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT .

00 − x) (1. Use of ICE charts are best illustrated by way of examples.23 × 102 = x (1. (8.23 × 102 .00 M. Example 1: Consider the reaction A(aq) + 2B(aq) C(aq) . We set-up our ICE chart A B C I 1.00 0 −x −2x x C E 1. ICE CHARTS 33 . and the “E” stands for equilibrium concentration. These calculations can be aided through the used of an ICE chart. Initial concentrations of A and B are each 1.00 − 2x x We now use the equilibrium constant.1) where K = 1. the “C” stands for change in concentration.00 − 2x)2 (8.00 1.3) Unfortunately we are now faced with a cubic equation to solve. Determine the concentration of reactants and products at equilibrium. The “I” stands for initial concentration. K = 1.2) We can rearrange this to give 492x3 − 984x2 + 616x − 123 = 0 (8.8 ICE CHARTS One of the most important things to be able to do with the equilibrium constant is to calculate the concentration of products and reactants at equilibrium given an initial concentration of reactants.00 − x 1.

only the x = 0.23 × 10−1 .423x − 0.7) (x) (x) (0.333 0 C −x x E 0.459 = 0.00 − 2 × 0.00 − 0.141 = 0 (8.459 solution makes sense.8) ICE CHARTS .6) C 0 x x This is a quadratic equation so we can easily get the solutions via the quadratic formula.23 × 10−1 = This can be rearranged into x2 + 0.333 − x x The equilibrium equation is Kp = 4.This is hard to solve algebraically but you can use your calculators to get three solutions: x = 0.992.459. The initial partial pressure of A is 0.333 atm. First we set-up the ICE chart A B I 0.333 − x) (8.4) where Kp = 4. Only one of these solutions can be the real answer. x = 0. The other solutions give a negative concentration for B. Since the ﬁnal concentration of B is 1.5) (8. bx ax2 + √ + c = 0 b ± b2 − 4ac x = − 2a 34 (8. Determine the concentration of reactants and products at equilibrium.459 = 0.541 M [B] = 1. We can ﬁgure that out by inspection.550. x = 0. Thus the ﬁnal equilibrium conditions are [A] = 1.459 M Example 2: Consider the reaction A(g) B(g) + C(g) . (8.082 M [C] = 0.00 − 2x.

Why does this work? Can you think of situations where it would not work? 2. 23 ICE CHARTS 35 .4.333 − 0. 21.4232 − 4 (0.9) Again. x = 0.642.219.219 = 0.141) x = − 2 x = −0. 15. 17.219 atm PC = 0. Normally when we use the stoichiometry of a reaction we must compare moles. The ﬁnal equilibrium conditions are PA = 0. 14. we need to determine the real solution by inspection.10) Group Work 1. 19. 0. Use the ideal gas law to derive the relationship between K and KP : KP = K(RT )4n . Homework Reading: Kotz and Treichel.219 atm (8.219 is our solution. 16. 18. 16.5 Problems: Chapter 16: 13.For this example.114 atm PB = 0.423 ± (8. p 0. A negative x does not make physical sense so x = 0. but the ICE chart uses concentration directly.

36 ICE CHARTS .

2) The reaction quotient applies to the current situation of the reaction and thus changes over the course of the reaction. [products] Q= . if Q > K the reaction will proceed in the reverse direction (make more reactants). however. Clearly. Beyond that. (9. It turns out that one can extend the deﬁnition of the equilibrium constant to non-equilibrium situations. at equilibrium Q = K. THE REACTION QUOTIENT AND LECHATELIER’S PRINCIPLE 37 .9 THE REACTION QUOTIENT AND LECHATELIER’S PRINCIPLE We have seen that the equilibrium constant is an important quantity.3) (9. the reaction quotient is Q= [C]c [D]d [A]a [B]b .1) [reactants] So. for the reaction. (9. The Reaction Quotient Under non-equilibrium situations the ratio of the concentration (or partial pressures) of products to reactants is called the reaction quotient. aA + bB cC + dD. if Q < K the reaction will proceed in the forward direction (make more products). And.

LeChatelier’s Principle One of the most important concepts in equilibrium is LeChatelier’s principle which describe how systems behave when they are taken out of equilibrium LeChatelier’s principle states that when any factor that determines the equilibrium condition of the system is changed. the system will respond in such a way to counteract and reduce the eﬀect of that change. if product is added the system the numerator of Q gets better and Q > K. Consider the reaction aA + bB cC + dD. Conversely if more product is added the system is shifted out of equilibrium to the product side. (9. At equilibrium Q = K. Similarly. Now consider adding more reactant A or B.4) 38 THE REACTION QUOTIENT AND LECHATELIER’S PRINCIPLE . LeChatelier’s principle says the system will respond by making more product. Takes the system out of equilibrium to the reactant side of the reaction. LeChatelier’s principle says the system will respond by going in reverse to make more reactant. at equilibrium. If reactant is added then the denominator of Q gets bigger and Q < K. We can capture LeChatelier’s principle mathematically by considering the reaction quotient. This Q < K condition says that the reaction will proceed forward.

Conversely if a reaction is endothermic we can think of heat as one of the reactants. If the temperature changes then K changes while Q stays the same. increasing the temperature will shift the reaction out of equilibrium in the product direction and the system will proceed towards reactants Here too we can view this property in terms of the reaction quotient. Temperature can also play a role. Group Work 1. if the system is at equilibrium at one temperature K = Q. For endothermic reactions K ↑ as T ↑ and for exothermic reactions K ↓ as T ↑ . So. it is the equilibrium constant that changes with temperature. however. Let’s say an important drug was produced in a reaction A + B Drug. but the equilibrium constant was small. Consequently. Suggest a way to use THE REACTION QUOTIENT AND LECHATELIER’S PRINCIPLE 39 . If a reaction is exothermic we can think of heat as one of the products. K 6= Q and the system will adjust accordingly. The reactants A and B are both very expensive.This Q > K condition says that the reaction will go in reverse. Now. For an endothermic reaction at equilibrium. increasing the temperature will shift the reaction out of equilibrium in the reactant direction and the system will proceed towards products For an exothermic reaction at equilibrium.

27. Use LeChatelier’s principle to get the most amount of drug for the least expense.LeChatelier’s principle to get the most drug for the least amount of reactant. 2. 26. 16. 49 40 THE REACTION QUOTIENT AND LECHATELIER’S PRINCIPLE . Consider the above problem but now A is very expensive but B is very cheap. 3. How would LeChatelier’s principle apply to gas phase reaction where the pressure is changed? Homework Reading: Kotz and Treichel. 41. 28. 43.8 Problems: Chapter 16: 25. 16. Also assume that your suggestion from above was diﬃcult to do in the lab for this drug.7.

10 REVIEW FOR EXAM 1 REVIEW FOR EXAM 1 41 .

Material for Exam II 42 REVIEW FOR EXAM 1 .

like H2 SO4 are called polyprotic acids. We will spend the next few lectures looking at acid—base reactions in the context of equilibrium Brønstad Acids and Bases Our ﬁrst deﬁnition of an acid or base is what called the BrønstadLowry concept of an acid or base. like HCl are called monoprotic acids.1) Here HA in it is the acid and B− is the base. Conjugate Acid-Base Pairs Within the Brønstad-Lowry concept of an acid or base. Brønstad acids that can donate more than one proton. A Brønstad acid is any compound that can donate a proton A Brønstad base is any compound that can accept a proton Brønstad acids that can donate one proton. HA + B− A− + HB (11. an acid— base reaction involves the transfer of a proton from the acid to the base.11 ACIDS AND BASES We are familiar with acids and bases and their reactions from last semester. ACIDS AND BASES 43 .

For polyprotic acids we must consider each proton donation separately. So within the reaction HA and A− form a so-called conjugate acid-base pair.We could write the reaction in reverse. the stronger one partner is. So a strong acid has a corresponding weak conjugate base and a weak acid has a strong conjugate base. the weaker the other partner is. Likewise B− and HB form a conjugate pair. For conjugate acid base pairs. H2 A + B2− HA− + HB− A2− +H2 B.2) Group Work 1. Identify the conjugate acid-base pairs in the following reactions 44 ACIDS AND BASES . Here the conjugate pairs are H2 A HA− HB− H2 B ⇐⇒ ⇐⇒ ⇐⇒ ⇐⇒ HA− A2− B2− HB− (11. Give the conjugate partner for (a) HNO3 (b) H2 CO3 (c) HCO− 3 (d) NH3 (e) H2 O 2. A− + HB HA + B− Now A− is the base and HB is the acid.

1. H2 NCHCOOH. The nitrogen end can act like a Brønstad base by accepting another proton whereas the oxygen end can act like a Brønstad acid by giving up the proton attached to it. 7 ACIDS AND BASES 45 . 3. Write two separate reactions of glycine ﬁrst with a Brønstad acid and then with a Brønstad base. 17. 5.2 Problems: Chapter 17: 1. Amino acids have an interesting structure in that they all have a region that acts like and acid and a region that acts like a base.(a) (b) CH3 CO2 H + NH3 CH3 CO− + NH+ 2 4 H2 S + H2 O HS− + H3 O+ 3. Homework Reading: Kotz and Treichel. The simplest amino acid is glycine. 6. 2. 17.

46 ACIDS AND BASES .

At standard conditions of 25 ◦ C.12 WATER AND PH We learned about the pH scale last semester and we saw that it was a result of the fact that water is a weak electrolyte.2) If we now consider the addition of an Brønstad acid to water.0 × 10−7 . we see that the H3 O+ goes up: Q > Kw . 2H2 O(l) H3 O+ + OH− (aq) (aq) (12. then for pure water ¤ £ ¤ £ H3 O+ = OH− = 1.1) Notice that we do not include the concentration of H2 O because it a considered a pure liquid. That is water under goes autoionization. the autoionization is driven backwards. By the symmetry of the reaction. (12. More £ precisely the autoionization reaction is driven backwards ¤£ ¤ until H3 O+ OH− = Kw . H3 O+ + OH− → 2H2 O(l) . A similar situation arrises for addition of a Brønstad base. two water molecules creates one H3 O+ and one OH− . We can write the equilibrium constant for this reaction as £ ¤£ ¤ K = Kw = H3 O+ OH− . £ ¤£ ¤ Kw = 1. By LeChatelier’s principle. Therefore the concentration of OH− goes down.0 × 10−14 = H3 O+ OH− . WATER AND PH 47 . (aq) (aq) The only source of OH− is from the original water.

¡ ¢ ¡£ ¤£ ¤¢ − log Kw = − log 1. Example 1: What is the pH of a 2. it fully dissociates to produce a 2. determination of pH is relatively easy based on the LeChatelier arguments above.3 × 10−3 = 2.3×10−3 M solution of HCl. Consider taking the negative log of Kw .3 × 10−3 = 2.0 × 10−14 = − log H3 O+ OH− £ ¤ ¤ £ 14 = − log H3 O+ − log OH− | {z }| {z } pH pOH 14 = pH + pOH The pH of Strong Acids and Bases If one is dealing with strong acids and bases.36 48 WATER AND PH From the 14 =pH + pOH relationship .The pH Scale £ ¤ £ ¤ The inverse relationship between H3 O+ and OH− is seen in the pH scale.63 pH = 14 − 2. The pOH is ¢ ¡ pOH = − log 2.3 × 10−3 M solution of H3 O+ .3 × 10−3 M solution of H3 O+ . Since HCl is a strong acid. The pH is simply ¢ ¡ pH = − log 2.63 Example 2: What is the pH of a 2.63 = 11. it fully dissociates to produce a 2. Since NaOH is a strong base.3 × 10−3 M solution of NaOH.

29 × 10−14 25 1. 2.00 × 10−14 50 5.3.Group Work 1. What is the pH of a 4. 11. 14 WATER AND PH 49 . Identify the conjugate pairs in the autoionzation reaction for water. why not? Homework Reading: Kotz and Treichel. 12. 13.48 × 10−14 (a) Is the autoionization reaction exothermic or endothermic? (b) What is the pH range at 50 ◦ C? 3.56 × 10−2 M solution of HNO3 ? 4. 10. Considering the Kw data for diﬀerent temperatures given in the table below ◦ C Kw 10 0.89 × 10−10 M solution of KOH? Does this answer make any sense? If not. 17. What is the pH of a 7. Problems: Chapter 17: 9.

50 WATER AND PH .

1) (13. BOH B+ + OH− . The larger the Ka the stronger the acid Likewise for a weak base equilibrium reaction.13 ACID AND BASE EQUILIBRIA Up until now we have been considering strong acids and bases in which the acid or base fully dissociates. ACID AND BASE EQUILIBRIA 51 .5) (13. etc. (13. Ka2 .) for each of the dissociation reactions.3) (13. For weak acids and bases we must set-up an equilibrium expression.4) If the acid (or base) is polyprotic then there are multiple Ka values (Ka1 . There is a relationship between Ka and Kb for conjugate acid— base pairs. The relationship is Ka Kb = Kw . For a weak acid equilibrium reaction.2) (13. HA H+ + A− . the equilibrium expression is £ +¤ £ −¤ A H Ka = [HA] where Ka is called the acid dissociation constant. the equilibrium expression is £ −¤ £ +¤ B OH Kb = [BOH] where Kb is called the base dissociation constant.

11) Example 2: What is the pH of a 0.1 × 10−5 . [HC6 H4 NO2 ] I 0. as will often be the case Ka1 À Ka2 so Ka1 alone will determine the pH. However.4 × 10−5 = (x) (x) (0. x x x x (13. 52 ACID AND BASE EQUILIBRIA . Ka1 Ka2 £ +¤ £ −¤ HA H .10) ¡ ¢ pH = − log 4. The Ka1 = 7.6) Example 1: Calculate the pH of a 0.6 × 10−12 . for this case. 2 Next we setup an ICE chart.012 M solution of niacin (HC 6 H 4 NO 2 ).012 − x) (13. = [H2 A] £ + ¤ £ 2− ¤ A H £ −¤ = HA (13.7) (13.8) Therefore the Rearranging and solving for x using the quadratic formula we get £ ¤ x = H+ = 4. (13.10 M solution of vitamin C (H 2 C 6 H 6 O 6 ).4 × 10−5 .9 × 10−5 and Ka2 = 1. The Ka = 1. We ﬁrst write the appropriate equilibrium reaction HC6 H4 NO2 H+ + C6 H4 NO− .39 (13. Ka = 1.012 − x From Ka we get the equation.9) £ +¤ £ ¤ H C6 H4 NO− 2 0 0 . In general this problem is more complicated because of the two Ka values. For polyprotic acids (or bases) we must consider separate equilibrium reactions H2 A H+ + HA− HA− H+ + A2− where.Usually Ka1 À Ka2 À Ka3 .1 × 10−5 = 3.012 C −x E 0.

Like above we ﬁrst write that appropriate reaction. (0. The ICE chart is £ ¤ £ +¤ £ ¤ HC6 H6 O− H C6 H6 O2− 6 6 I 0.7 × 10−8 6 ACID AND BASE EQUILIBRIA 53 .9 × 10−5 = (x) (x) . Now we do need the second dissociation reaction HC6 H6 O− H+ + C6 H6 O2− 6 6 and we setup and ICE chart where we use the ¤ £ x = HC6 H6 O− = 0.0028 6 result from example 2.55 Example 3: Calculate the concentration of C 6 H 6 O 2− for the 6 case of example 2.6 × 10−12 = and solving to get (y) (y) (0.0028 0 0 .10 C −x E 0. pH = − log (0.0028 − y Utilizing Ka2 = 1.0028 − y) £ ¤ y = C6 H6 O2− = 6. C −y y y y y E 0.0028) = 2.10 − x) £ +¤ £ ¤ H HC6 H6 O− 6 0 0 x x x x Therefore the Rearranging and using the quadratic formula gives £ ¤ x = H+ = 0. H2 C6 H6 O6 H+ + HC6 H6 O− 6 and produce an ICE chart [H2 C6 H6 O6 ] I 0.0028.10 − x The Ka1 equation gives Ka1 = 7.

31 54 ACID AND BASE EQUILIBRIA .3 × 10−8 . What is the pH of a 0.Group Work 1. 17. 29.3 × 10−2 and Ka2 = 6. The Kb = 1.4 Problems: Chapter 17: 15. 21. 27. 17. What is the equilibrium concentration of SO2− if one ini3 tially prepares a 0. 3.7 × 10−6 . Homework Reading: Kotz and Treichel.100 M solution of H2 SO3 ? The Ka values are: Ka1 = 1. hydrazine (N2 H2 ). 19.10 M solution of the base. What is the pKa for niacin and what are the pKa1 and pK2 values for vitamin C? 2. 23. 25.

REACTIONS WITH WEAK ACIDS AND WEAK BASES 55 . We will take the reactants to be present in stoichiometric ratios.1) We know that sodium hydroxide is a strong base so it fully dissociates to produce OH− . We will not consider limiting reagent cases until later. HC6 H4 NO2 + NaOH NaC6 H4 NO2 + H2 O. Reaction Between a Monoprotic Weak Acid and a Strong Base We ﬁrst consider a reaction between a weak monoprotic weak acid with a strong base. Since this is a reaction between a weak base and a strong base we would expect the ﬁnal pH to be basic.14 REACTIONS WITH WEAK ACIDS AND WEAK BASES We have learned how to determine the pH of a weak acid or weak base solution.2) (14. For niacin the Ka = 1.4 × 10−5 . Example: What is the ﬁnal pH if 25 ml of a 0. We will now extend that to include calculating the pH after a acid—base reaction. 2 (14.10 M niacin (HC 6 H 4 NO 2 ) is reacted with 25 ml of 0.10M NaOH. We ﬁrst write a balanced reaction. It is convenient to express the net ionic equation. HC6 H4 NO2 + OH− C6 H4 NO− + H2 O.

0. the ICE chart is £ £ ¤ ¤ C6 H4 NO− [HC6 H4 NO2 ] OH− 2 I 0.0025 mol C6 H4 NO− £ 2 − = 0. The reaction between a weak base and a strong acid would be done in a similar manner. Kw = 7. we have Kb = 7.78. 2 To do this we see.050 L Using this. (14. but since this is the conjugate 2 base to a weak acid we must set-up a base dissociation reaction C6 H4 NO− HC6 H4 NO2 + OH− . From this ¡ ¢ pOH = − log 5. 56 REACTIONS WITH WEAK ACIDS AND WEAK BASES . 2 The Kb for this reaction is obtain from the Ka for niacin and Kw . C −x x x E 0.05 0 0 .10 mol HC6 H4 NO2 = 0.05 M C6 H4 NO− C6 H4 NO2 = 2 0.97 × 10−6 = 5.14 × 10−10 .10 mol HC6 H4 NO2 2 × × L 0. pH = 14 − 5.14 × 10−10 = (x) (x) (0.All of the OH− reacts with the H+ from niacin.05 − x x x So. ¤ 0.10 mol C6 H4 NO− 0.3) Kb = Ka We will need to setup and ICE chart but ﬁrst we must determine the concentration of C6 H4 NO− .05 − x) Hence.22. Now this leaves only C6 H4 NO− .97 × 10−6 .22 = 8.0025 mol C6 H4 NO− 2 But we also had 25 mL from the NaOH solution so the total volume is now 50 mL thus. Rearranging and using the quadratic formula we get x = [OH] = 5.025 L HC6 H4 NO2 0.

6 The Kb ’s are obtained from the Ka ’s.10 M Vitamin C (H 2 C 6 H 6 O 6 ) solution and 25 mL of a 0.20 M NaOH solution? The Ka1 = 7.05 − x x x REACTIONS WITH WEAK ACIDS AND WEAK BASES 57 .05 M C6 H6 O2− .10 mol H2 C6 H6 O6 0. 6 6 0.Reaction Between a Polyprotic Weak Acid and a Strong Base The reaction of a weak polyprotic acid and a strong base is a little more complicated but is nonetheless similar to what we have done. Ka2 We need to now consider the weak base equilibrium of C6 H6 O2− .050 L Kw = 1. Example: What is the ﬁnal pH of a reaction between 25 ml of a 0.0025 mol C6 H6 O2− 6 C6 H6 O2− = = 0.025 L H2 C6 H6 O6 0. £ ¤ 0.2 × 10−10 Ka1 Kw = = 6.3 × 10−3 . Kb1 = Kb2 Since Kb2 À Kb1 .6 × 10−12 . C −x x x E 0.9 × 10−5 and Ka2 = 1. The concentration of C6 H6 O2− is 6 6 0.05 0 0 .10 mol C6 H6 O2− 6 × × L 0.0025 mol C6 H6 O2− 6 The total volume after the reaction is 50 mL so. Like above we write a balanced reaction H2 C6 H6 O6 + 2NaOH Na2 C6 H6 O6 + 2H2 O H2 C6 H6 O6 + 2OH− C6 H6 O2− + 2H2 O 6 All the NaOH reacted with the vitamin C to produce only C6 H6 O2− .10 mol H2 C6 H6 O6 = 0. we need only consider the reaction C6 H6 O2− HC6 H6 O− + OH− 6 6 and the ICE chart is £ ¤ £ ¤ £ −¤ C6 H6 O2− HC6 H6 O− OH 6 6 I 0.

4 × 10−5 2 NH3 + H2 O NH+ + OH− Kb = 1.3 × 10−3 = £ ¤ Rearranging and using the quadratic formula we get x = OH− = 0.8 × 10−5 4 H+ + OH− H2 O 1/Kw = 1.05 − x) Reaction Between a Weak Acid and a Weak Base The reaction between a weak acid and a weak base requires a diﬀerent strategy since we can not exploit the full dissociation of the strong acid or base as we did above. 58 REACTIONS WITH WEAK ACIDS AND WEAK BASES .18 (x) (x) (0. ﬁnally.5 × 10+4 Kw Upon mixing the volume of the solution is doubled so the initial concentrations are half of what they are prior to mixing.4 × 10−5 ) is reacted with 25 ml of a 0.82.015 and pOH = − log (0. 2 4 We now use Hess’ law to write HC6 H4 NO2 H+ + C6 H4 NO− Ka = 1.From this Kb2 = 6. Example: What are the ﬁnal concentrations of products if 25 ml of a 0. pH = 14 − 1. we start with a balanced equation HC6 H4 NO2 + NH3 C6 H4 NO− + NH+ . We can perform this calculation by using Hess’ law from last semester.015) = 1.10 M niacin solution ( Ka = 1.10 M NH 3 solution ( Kb = 1.82 = 12. So.8 × 10−5 )? As before.0 × 10+14 This gives the original reaction and the equilibrium constant for this reaction is K= Ka Kb = 2.

[HC6 H4 NO2 ] [NH3 ] ¤ £ C6 H4 NO− £ 2¤ NH+ 4 Work Group 1. Homework Reading: Kotz and Treichel. 37.0496 0.05 − x) = = = = 0. 17. 67 REACTIONS WITH WEAK ACIDS AND WEAK BASES 59 . 17.05 − x 0. 41.0496.7.We can then setup an ICE chart as £ ¤ £ +¤ [HC6 H4 NO2 ] [NH3 ] C6 H4 NO− NH4 2 I 0. What is the ﬁnal pH if 25 ml of a 0.8 × 10−5 .8.10 M ammonia solution is reacted with 25 ml of 0.10 M HCl? For ammonia the Kb = 1. So.05 − x x x Thus.05 − x) (0. 17. K = 2.0496 M M M M Rearranging a solving for x gives x = 0.05 0 0 C −x −x x x E 0.5. 61.0004 0. 17. 49. 65.6. 17.5 × 10+4 = (x) (x) (0.0004 0. 39.05 0.9 Problems: Chapter 17: 35.

60 REACTIONS WITH WEAK ACIDS AND WEAK BASES .

15THE COMMON ION EFFECT AND BUFFERS It is important to consider an acid dissociation reaction (or base reaction) in which a compound that contains one of the product ions is added HA H+ + A− add H+ or A− .0028 + x x THE COMMON ION EFFECT AND BUFFERS 61 .01 mol H+ 1 × = 0. By LeChatelier’s principle the reaction is shifted back towards the reactant.035 L × We now can setup an ICE chart.071 M HC6 H4 NO2 1L 0. C −x x x E 0. common ion.0028 0 .071 0.071 − x 0.035 L and 0.10 M niacin (HC 6 H 4 NO 2 ) solution ( Ka = 1.1 mol HC6 H4 NO2 1 × × = 0. The new volume is 35 mL so.010 M HCl is added to 25 mL of a 0.4 × 10−5 )? We ﬁrst need to determine the initial concentrations of niacin and the.025 L 0. This shift in the equilibrium by LeChatelier’s principle is called the common ion eﬀect. £ +¤ £ ¤ [HC6 H4 NO2 ] H C6 H4 NO− 2 I 0. 0.01 L 0. H+ upon mixing.0028 M H+ 1L 0. Example: How does the equilibrium shift when 10 mL of 0.

With the Ka value we can get the equilibrium concentrations, Ka = 1.4 × 10−5 = (0.028 + x) (x) . (0.071 − x) (15.1)

Rearranging and using the quadratic formula we get x = 3.2 × 10−4 . Hence [HC6 H4 NO2 ] = 0.071 − 3.2 × 10−4 = 0.071 £ +¤ = 0.0028 − 3.2 × 10−4 = 0.0025 H ¤ £ C6 H4 NO− = 3.2 × 10−4 2

Buﬀer Solutions

An important application of the common ion eﬀect occurs when the common ion is the conjugate pair to the original acid or base. These solutions are called pH buﬀer solutions (or buﬀers for short) and they have the valuable property that one can add a strong acid or base to a buﬀer and not change the pH signiﬁcantly. The human body makes use of many buﬀers to control the pH of the extra- and intra- cellular environments. Example, the acetate buﬀer (part 1): Calculate the pH of an acetate buﬀer that is prepared by adding 25 ml of a 0.10 M acetic acid (HC 2 H 3 O 2 ) solution to 15 mL of 0.10 M of a sodium acetate (NaC 2 H 3 O 2 ) solution ( Ka = 1.7 × 10−5 ). We ﬁrst determine the initial concentrations of acetic acid and acetate ion, 1 0.10 mol HC2 H3 O2 × = 0.063 M HC2 H3 O2 1L 0.040 mL 0.015 L 0.10 mol C2 H3 O− 1 2 × = 0.038 M C2 H3 O− , × 2 1L 0.040 mL then setup an ICE chart £ ¤ £ ¤ [HC2 H3 O2 ] H+ C2 H3 O− 2 I 0.063 0 0.038 . C −x x x E 0.063 − x x 0.038 + x ×

62 THE COMMON ION EFFECT AND BUFFERS

0.025 L

Using, (x) (0.038 + x) , (0.063 − x) £ ¤ and the quadratic formula, we get x = H+ = 2.8 × 10−5 . So, ¡ ¢ pH = − log 2.8 × 10−5 = 4.55. Ka = 1.7 × 10−5 =

Example, the acetate buﬀer (part 2): Calculate the pH if 10 ml of 0.01 M HCl is added to the above buﬀer. Then compare this to the pH if the HCl was added to water. First we ﬁgure out how many moles of H+ is coming from the HCl, 0.010 L 0.010 mol H+ × = 0.0001 mol H+ . 1L We take it that all the H+ reacts with C6 H4 NO− to make 2 HC2 H3 O2 . Thus we must determine the new concentrations of C6 H4 NO− and HC2 H3 O2 . 2 From above we know the equilibrium concentrations of C6 H4 NO− 2 and HC2 H3 O2 before the HCl is added. These are [HC2 H3 O2 ] = 0.063 − 1.7 × 10−5 = 0.063 M ¤ £ C2 H3 O− = 0.038 + 1.7 × 10−5 = 0.038 M 2

So the number of moles of each present are

0.063 mol HC2 H3 O2 0.040 L × = 0.0025 mol HC2 H3 O2 1L and 0.038 mol HC2 H3 O2 0.040 L × = 0.0015 mol C2 H3 O− . 2 1L After completely reacting with the 0.0005 mol of H+ from the HCl we have 0.0025 + 0.0001 = 0.0026 mol HC2 H3 O2 and 0.0015 − 0.0001 = 0.0014 mol HC2 H3 O2 . Now we need to get the new concentrations 0.0026 mol HC2 H3 O2 = 0.052 M HC2 H3 O2 0.050 L

THE COMMON ION EFFECT AND BUFFERS 63

and

0.0014 mol C2 H3 O− 2 = 0.028 M C2 H3 O− . 2 0.050 L Finally we now need to setup an ICE chart, £ ¤ £ ¤ [HC2 H3 O2 ] H+ C2 H3 O− 2 I 0.052 0 0.028 . −x x x C E 0.052 − x x 0.028 + x Using Ka = 1.7 × 10−5 =

So a change in pH of only 0.05 units.

(x) (0.028 + x) (0.052 − x) £ ¤ and solving the quadratic equation we get x = H+ = 3.15 × 10−5 . So, ¢ ¡ pH = − log 3.15 × 10−5 = 4.50

We now calculate the pH for the situation of adding the HCl to pure water. From above we see that 0.0001 mol of H+ are produced. These moles are now in a total volume of 40 mL so, £ + ¤ 0.0001 mol H+ = 0.0025 M H = 0.040 mL pH = − log (0.0025) = 2.60, which is a change of 4.55 − 2.60 = 1.95 units.

Hence a pH of

Group Work

1. Calculate the pH change when 15 ml of 0.0010 M NaOH is added to the buﬀer of the example in lecture. 2. What is the pH of an ammonium buﬀer that is made by mixing 50 mL of a 0.50 M NH3 solution with 50 mL of a 0.30 M NH4 Cl solution?

64 THE COMMON ION EFFECT AND BUFFERS

3. It will be important to be able to work the above buﬀer calculations in a diﬀerent way so that we can prepare a buﬀer of a desired pH. Prepare 100 ml of a acetate buﬀer with a pH of 4.25. £ ¤ (a) First use the pH ﬁnd H+ £ ¤ (b) Now you ¤know H+ and Ka . Solve for the ratio, £ C2 H3 O− / [HC2 H3 O2 ] . Any 100 ml solution that 2 has this ratio of concentrations will give the desired pH.

Homework

Reading: Kotz and Treichel, 18.1, 18.2 Problems: Chapter 18: 1, 5, 7, 8, 19, 21

THE COMMON ION EFFECT AND BUFFERS

65

66 THE COMMON ION EFFECT AND BUFFERS .

7 × 10−5 )? MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION 67 .2) Now if we take of the negative log of the Ka equation. it is important to be able to make buﬀers of a desired pH.25 ( Ka = 1. HA H+ + A− .1) Ka = [HA] for the buﬀer equilibrium.16 MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION As we learned from the third group work question last time. £ +¤ £ −¤ A H . If we consider the Ka equation for a buﬀer situation we have. Example 1: How would you make an acetate buﬀer that has a pH of 4. [HA] We can use the Henderson—Hasselbalch equation to short-cut our buﬀer calculations. we get Ã£ ¤ £ ¤! H+ A− − log Ka = − log [HA] Ã£ ¤! £ +¤ A− − log Ka = − log H − log | {z } [HA] | {z } pKa pH Ã£ ¤! A− pKa = pH − log [HA] Solving for pH gives the Henderson—Hasselbalch equation: Ã£ ¤! A− pH = pKa + log . (16. (16.

7 × 10−5 = 4.52 = 0.1 pH unit around the pKa of acetic acid. Technically we should back calculate from the equilibrium concentrations to the initial concentrations. Why? 4.52 log [HC2 H3 O2 ] Ã£ ¤! C2 H3 O− 2 = 10−0.25 − 4.77 Group Work 1. What would the pH of an acetate buﬀer made by combining 50 mL of a 1. pKa = − log 1.30.25 M NaC2 H3 O2 solution? 3.2 M solution of HC2 H3 O2 with 50 mL of a 0. for buﬀers the equilibrium concentrations of the acid and the conjugate base do not diﬀer signiﬁcantly from the starting concentrations. 50 mL of a 0. Thus one way to make this buﬀer would be to mix. What is the acceptable [C2 H3 O− ] 2 range of the ratio [HC2 H3 O2 ] ? 68 MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION .00 M HC2 H3 O2 solution with 50 mL of a 1. say. It is a good idea to choose an acid base conjugate pair that has a pKa that is near to the pH that one is trying to make a buﬀer for. How would you make an acetate buﬀer that has a pH of 5.06 M solution of NaC2 H3 O2 . Let say you wanted to hold your pH to within 0.30 [HC2 H3 O2 ] This tells use that at equilibrium the ratio must be 0.00 (Ka = 1.25 = 4. However.77 + log [HC2 H3 O2 ] Ã£ ¤! C2 H3 O− 2 = 4.The Using the Henderson—Hasselbalch equation we have Ã£ ¤! C2 H3 O− 2 4.77 = −0.7 × 10−5 )? 2.

13. 15. 17. 18 MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION 69 .Homework Problems: Chapter 18: 11.

70 MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION .

17 TITRATIONS PART I Last semester in lab and in lecture we gained some experience with titrations.100 mol HCl = 0. i) before the equivalence point. This titration reaction is HCl + NaOH NaCl + H2 O The total number of moles of HCl is 0. is that involving a strong acid and a strong base.100 M NaOH.025 L × 0. ii) the equivalence point and iii) after the equivalence point.2) (17. We learned that titrations are important techniques for determining the concentration of the analyte. Titration of a Strong Acid with a Strong Base The simplest case of a titration reaction. We now revisit titrations armed with our knowledge of acid— base equilibria. and one we could handle last semester.1) This problem breaks into three parts.100 M HCl solution is titrated with 0. TITRATIONS PART I 71 . Calculate the titration curve for this process. Example: 25 mL of a 0. Since both the analyte and the titrant are strong electrolytes they fully dissociate and therefore fully react.0025 mol HCl 1L (17.

025 L NaOH × 1 mol HCl 0.0025 pH = 14 − − log 0. ∙ µ ¶¸ 0.025 + Y ¶ µ 0.025 + X (17.025 + Y (17. Thus 0.5) After the equivalence point HCl is the limiting reactant.3) have reacted with the HCl. This occurs at 0.025 + X ¶ µ 0.1Y mol NaOH 1L (17.Before the equivalence point NaOH is the limiting reagent.0025 mol NaOH unreacted.0025 pOH = − log 0.100 mol NaOH (17.1X moles of HCl remains.1X pH = − log 0.0025 − 0.0025 OH = 0.0025 mol HCl 1 mol NaOH 1 L NaOH × = 0.025 + Y Thus.1Y − 0. From this £ −¤ 0. Then.1Y − 0. If X L of NaOH is added then 0. Of these moles 0.100 mol NaOH = 0.8) The titration curve is shown in the ﬁgure below 72 TITRATIONS PART I .4) At the equivalence point the HCl and NaOH exactly neutralize one another and the pH= 7. If Y L of NaOH is added then Y L NaOH × 0.100 M NaOH X L = 0.1X H = 0.1Y − 0.0025 mol react with the HCl leaving 0.1Y − 0.00.0025 − 0.1X mol NaOH × 1L (17.6) have been added. £ +¤ 0.0025 − 0.7) (17.

14 12 10 8

pH

6 4 2 0 0 10 20 30 40 50

mL NaOH added

**Titration of a Weak Acid with a Strong Base
**

This situation is complicated by the need to determine the dissociation equilibrium for the weak acid. We have, however, learned enough to handle this problem. Example: Calculate the titration curve when 25 mL of a 0.10 M niacin (HC 6 H 4 NO 2 ) solution, Ka = 1.4 × 10−5 , is titrated with 0.10 M NaOH. As with strong acid, strong base titrations we need to split the problem into three parts: (i) before the equivalence point, (ii) the equivalence point, and (iii) after the equivalence point. The total number of moles of HCl is 0.025 L 0.100 mol HC6 H4 NO2 = 0.0025 mol HC6 H4 NO2 × 1L (17.9) Before the equivalence point NaOH is the limiting reagent. Let’s say X mL of NaOH is delivered thus 0.1X mol of NaOH reacts fully with the niacin.

TITRATIONS PART I 73

This leaves 0.0025−0.1X mol of niacin and 0.1X mol of C6 H4 NO− 2 The concentrations acetic acid and acetate ion are 0.0025 − 0.1X 0.025 + X and respectively. Now we setup an ICE chart I C E £ +¤ £ ¤ H C6 H4 NO− 2 0.0025−0.1X 0.1X 0 0.025+X 0.025+X −x x x 0.0025−0.1X 0.1X −x x +x 0.025+X 0.025+X [HC6 H4 NO2 ] 0.1X 0.025 + X

Using in the Ka we can solve for x which gives the H+ concentration, ¢ ¡ 0.1X + x (x) 0.025+X −5 ¢. Ka = 1.4 × 10 = ¡ 0.0025−0.1X −x 0.025+X The total volume is now 50 mL and there are 0.0025 mol of acetate ion, which is 0.0025 = 0.05 M 0.050 We use this in an ICE chart for the conjugate base reaction C6 H4 NO− + H2 O HC6 H4 NO2 + OH− , 2 £ £ ¤ ¤ C6 H4 NO− [HC6 H4 NO2 ] OH− 2 I 0.05 0 0 C −x x x E 0.05 − x x x

At the equivalence point and equal amount of NaOH has fully reacted with the niacin.

**Now since this is the conjugate base reaction we must use the Kb which is Kw Kb = = 7.1 × 10−10 . Ka So, (x) (x) . Kb = 7.1 × 10−10 = 0.05 − x
**

74 TITRATIONS PART I

Rearranging and using the quadratic formula gives x = [OH− ] = 6.0 × 10−6 . The pH is then ¤¢ ¡ £ pH = 14 − − log 6.0 × 10−6 = 8.78

Notice that the pH at the equivalence point is not 7.0 as it is in the case of a strong acid strong base titration. After the endpoint the niacin is the limiting reagent. So the problem becomes exactly like the strong acid strong base case. We ﬁgure out how much OH− is left over and get the pH from that.

Group Work

1. Calculate several values for the strong acid strong base titration example 2. Calculate several values for the weak acid strong base titration example 3. What is the pH at the equivalence point for the titration of 25 mL of 0.10M NH3 with HCl.

Homework

Reading: Kotz and Treichel, 18.3 Problems: Chapter 18: 23, 24, 25, 29, 79, 83 *Note* these are not due until after the next lecture.

TITRATIONS PART I

75

76 TITRATIONS PART I .

we will simply calculate the pH at each equivalence point.0025 mol HC6 H6 O− .9×10−5 reaction. This occurs at 25 mL of NaOH added. Instead.10 M NaOH.10 M solution of vitamin C (H 2 C 6 H 6 O 6 ) is titrated with 0. The Ka1 = 7. So we take the NaOH to fully react with the ﬁrst proton of vitamin C. Because Ka1 À Ka2 we take separate the process into two parts: Reaction with the ﬁrst equivalent of acid H2 C6 H6 O6 + NaOH NaHC6 H6 O6 + H2 O and the reaction with the second equivalent of acid NaHC6 H6 O6 + NaOH Na2 C6 H6 O6 + H2 O The problem is now like what we have done for monoprotic acids so we will not go through every detail. 0.6 × 10−12 . The ﬁrst equivalence point is controlled by the Ka1 = 7.9 × 10−5 and Ka2 = 1. 6 1L 77 TITRATIONS PART II . Or.18 TITRATIONS PART II With lecture and the group work problems we have tackled titrations with monoprotic acids and bases.10 mol HC6 H6 O− 6 = 0.025 L × 0. Now we will complete the picture with the titration of weak polyprotic acids (or bases) with strong bases (or acids) Example : Calculate the titration curve when 25 ml of a 0. Now the titration process will experience two equivalence points.

06 78 TITRATIONS PART II .0025 mol £ = 0. Thus pH = 14 − (− log [0.25 × 10−3 Kb2 = Ka2 The appropriate ICE chart for the reaction C6 H6 O2 + H2 O HC6 H6 O− + OH− 6 6 is £ ¤ £ −¤ £ ¤ C6 H6 O− OH HC6 H6 O− 6 6 I 0.05 0 0 C x x x 0.40 Now. ¡ £ ¤¢ pH = 14 − − log 2.075 L Now we need the Kb2 which is Kw = 6. C6 H6 O− = 6 0.27 × 10−10 Ka1 The ICE chart is £ ¤ £ −¤ HC6 H6 O− OH [H2 C6 H6 O6 ] 6 I 0.033 − x x x So.0025 mol HC6 H6 O− 6 = 0.050 L This HC6 H6 O− then goes back towards the acid via the conju6 gate base reaction.52 × 10−6 = 8. for the second equivalence point we repeat the procedure.05 M HC6 H6 O− 6 0.033 M. Thus.0116.52 × 10−6 . ¤ 0.Thus the concentration of HC6 H6 O− is 6 0.05 − x x x E £ ¤ Using the Kb1 equation and solving for x = OH− = 2.033 0 0 −x x x C E 0. HC6 H6 O− + H2 O H2 C6 H6 O6 + OH− 6 So we need the Kb1 which is Kw Kb1 = = 1. The second equivalence point occurs at the addition of a total of 50 mL of NaOH.0116]) 12. £ ¤ Using the Kb2 equation and solving for x we get x = OH− = 0.

3 Problems: Chapter 18: 23. 18. 29. Homework Reading: Kotz and Treichel. 24.Group Work 1. 83 TITRATIONS PART II 79 . Work out several values of the titration curve for the example above. 25. 79.

80 TITRATIONS PART II .

Lets say we want to know the concentration of Ca2+ and OH− upon putting solid Ca(OH)2 into a beaker. weak electrolytes and nonelectrolytes The solubility product gives us a way of ranking how soluble a compound is. quantitatively that Ca(OH)2 is more soluble then CaF2 .3 × 10−10 . For example of the solubility product for Fe2 (SO4 )3 is £ ¤2 £ ¤3 Ksp = Fe3+ SO2− 4 In the ﬁrst semester we simply learned ionic compounds as strong electrolytes. Remember the Anc Bna (s) is a solid so we do not include it in the equilibrium constant. £ ¤n £ ¤n Ksp = Ana + c B nc − a . SOLUBILITY OF WEAK ELECTROLYTES 81 . We can say. For example Ca(OH)2 has a Ksp of 5.19 SOLUBILITY OF WEAK ELECTROLYTES We have been applying our ideas about equilibrium to acid base reactions.5×10−5 whereas CaF2 has a Ksp = 5. But these ideas are general and apply to any reaction. Here we consider application to the solubility of weak electrolytes. Consider a general dissolution reaction na + nc − Anc Bna (s) nc A(aq) + na B(aq) The equilibrium constant for this reaction is called the solubility product.

We write the solubility reaction Ca(OH)2 Ca2+ + 2OH− and ¤£ ¤2 £ Ksp = 5.5 × 10 x = 4 x = 0. How would the common ion eﬀect work here? Can you setup an ICE chart that will handle the common ion eﬀect? 82 SOLUBILITY OF WEAK ELECTROLYTES .024 ¤ £ ¤ £ Thus Ca2+ = x = 0. pH = 14 − (− log 0.024 M and OH− = 2x = 0.5 × 10−5 = Ca2+ OH− From the stoichiometry of the reaction 2x moles of OH− is produced for every x moles of Ca2+ thus 5.5 × 10−5 x3 = r 4 −5 3 5.5 × 10−5 5. Group Work 1.6 We can take this further and determine the pH of the solution.048 M. The common ion eﬀect occurs in solubility reactions as well as acid-base reactions.5 × 10−5 = (x) (2x)2 4x3 = 5. Put the solubility reaction we did in class into the ICE chart formalism.048) pH = 12. Write the solubility product for (a) copper II sulﬁde (b) zinc II hydroxide (c) lead II iodide 2. 3.

59. 18. 47. 67 SOLUBILITY OF WEAK ELECTROLYTES 83 . 18. 53. 55. 39.Homework Reading: Kotz and Treichel. 18.5. 18.6.4.7 Problems: Chapter 18: 35. 65. 37. 45.

84 SOLUBILITY OF WEAK ELECTROLYTES .

20 REVIEW FOR EXAM 2 REVIEW FOR EXAM 2 85 .

Material for Exam III 86 REVIEW FOR EXAM 2 .

done on the system is by convention taken to be a positive quantity Any work done by the system is then negative.21 REVIEW OF THE FIRST LAW. But ﬁrst we need to review the key ideas from the ﬁrst semester. ENTHALPY. The ﬁrst law is stated mathematically as 4E = q + w. Any work. The First Law of Thermodynamics The ﬁrst law of thermodynamics is simply a statement of the conservation of energy for a system. AND HESS’ LAW Last semester we tackled several ideas from thermodynamics.1) Energy that enters or leaves a system is classiﬁed as either work or heat. As system here means any macroscopic piece of matter such as a beaker of water or an iron bar. REVIEW OF THE FIRST LAW. (21. ENTHALPY. w. we will complete the picture. over the next several lectures. In words the ﬁrst law states that a change in the total energy of a system is equal to the heat taken in by the system plus the work done on the system. AND HESS’ LAW 87 . Now.

AND HESS’ LAW . w < 0. q. ENTHALPY.Likewise any heat. Since we are adding heat to the system. q > 0. Since the system is doing work. 88 REVIEW OF THE FIRST LAW. taken in by the system is by convention a positive quantity (endothermic) Any heat given oﬀ by the system is negative (exothermic). Enthalpy Let us consider applying the ﬁrst law to a gas in a piston If we apply heat to the gas it expands against atmospheric pressure and in doing so it does work.

) Consider again the expanding gas example. Now if we add 10J of heat to the gas then 4H = 10J During a chemical reaction it is often rather convenient to measure the heat given oﬀ by a reaction. (21. AND HESS’ LAW 89 . ENTHALPY.The ﬁrst law for this case says 4E = q(positive) + w(negative) Therefore no matter what 4E < q (21. If 4H is negative that means that qP is negative and heat energy is given oﬀ by the system. REVIEW OF THE FIRST LAW. If we add 10 J of heat energy to the system the total energy does not change by 10 J This is somewhat inconvenient so chemists have deﬁned a new measure of energy called enthalpy (H) Enthalpy is deﬁned such that at constant pressure it is equal to the amount of heat energy taken in by the system 4H ≡ qP . Reactions with negative 4H are called exothermic reactions.4) where the subscript P reminds us that this is true only for constant pressure. you will do this in lab.2) So the change in total energy is less than the amount of heat energy we added to the system. In fact.5) If 4H is positive that means that qP is positive and heat energy is taken in by the system. (We will always work at constant pressure in this course. If the heat is measured at constant pressure then it is simply the change in enthalpy for the reaction: 4H = Hproducts − Hreactants (21.3) (21. Reactions with positive 4H are called endothermic reactions.

An important consequence of enthalpy being a state function is Hess’ law which states that if a reaction is the sum of two or more reactions.Hess’ Law Both total energy.7) (21. 4H for the reaction 2C6 H6 + 15O2 → 12CO2 + 6H2 O (21.8) (21. For example consider heating in water from 300 K to 310 K. For example.6) is the same as the sum of the 4H’s for the following reactions 2C6 H6 → 12C + 6H2 12C + 6H2 + 15O2 → 12CO2 + 6H2 O (21. AND HESS’ LAW . 90 REVIEW OF THE FIRST LAW. are what are called state functions A state function is a function that depends only on the particular state that the system is in. ENTHALPY. You would calculate the same 4H or 4E regardless as to whether you heated directly from 300 K to 310 K or if you ﬁrst cooled to 290 K then heated to 360 K and then cooled to 310 K. and enthalpy. H.9) Hess’s law is very handy because it would be impossible to measure enthalpy changes for every imaginable reaction were it not for Hess’ law. E. It is completely independent of how the system arrived at that state. 4H for the overall reaction is the sum of the 4H’s for the component reactions. That is 4H is solely determined by 4H = Hproducts − Hreactants regardless of how the reactants became the products.

ENTHALPY. 45. Based on your experience. 49. is 4H positive or negative for combustion reactions? 2. 53 REVIEW OF THE FIRST LAW. 4H = −91. 51. Use Hess’ law to determine 4Hrxn for 4NH3 + 5O2 → 4NO + 6H2 O given the following data N2 + O2 → 2NO. 4H = −483. AND HESS’ LAW 91 .Group Work 1.7 kJ 3. 43. 4H = 180.8 kJ 2H2 +O2 → 2H2 O.6 kJ N2 + 3H2 → 2NH3 . Based on the previous problem what is 4Hrxn for 5 2NH3 + O2 → 2NO + 3H2 O 2 Homework Problems: Chapter 6: 27. 47.

ENTHALPY. AND HESS’ LAW .92 REVIEW OF THE FIRST LAW.

This requires a few deﬁnitions. higher entropy means the system is disordered whereas low entropy means the system is ordered. There is an equally important concept in thermodynamics called entropy. This is idea of disorder is a good one and we should always keep it in mind but it does not capture all of the sublties about entropy Microstates and Conﬁgurations One can get a feel for entropy by considering the possible arrangements of the molecules in a system. Ensemble: The collections of molecules in a macroscopic system Microstate: One single arrangement of the ensemble Conﬁguration: Collection of indistinguishable microstates. for a given system. Given the symbol W ENTROPY 93 .22 ENTROPY Up to this point our discussion of thermodynamics has focussed on energy (either total energy or else enthalpy). A simple way of thinking about entropy is that it provides a measure of disorder in a system. That is.

Do you recognize the number? 4.Entropy: Proportional to the number of conﬁgurations through the Boltzmann equation S = k ln W. 5.3 Problems: Chapter 19: 1.2.1) Group Work 1.38 × 10−23 J/K is the Boltzmann constant. 19. Multiply the Boltzmann constant time Avogadro’ss number.3 94 ENTROPY .1. How does the number of microstates compare to the number of conﬁgurations? 2. where k = 1. How many diﬀerent ways are there to permute the letters in “CAT”? Call each permutation a microstate then collect equivalent microstates into conﬁgurations. The so-called thermal energy per molecule is kT . Homework Reading: Kotz and Treichel. Verify that it as proper units and calculate it for room temperature. The so-called thermal energy per mole is RT . Verify that it as proper units and calculate it for room temperature. ∗ ∗ ∗ WorkSheet on Microstate and Conﬁguration ∗ ∗∗ (22. 19. 19. Repeat the about for “ANN” 3.

(23. Natural processes can occur that lower the entropy of the system. Now it is important to realize that 4Ssys need not be greater than zero. The third law puts entropy on an absolute scale like temperature.3) (23. The statement of the third law is a little beyond what we are able to handle so we shall only consider the consequence of this mathematical statement. If this happens.1) For isolated systems in which no heat energy can be exchanged with the environment T 4S ≥ 0 4S ≥ 0. however. This leads to the important result that 4Suniverse = 4Ssys + 4Senv ≥ 0 (23. the change in entropy of the environment must be positive and outweigh that of the system. This is in contrast to energy which can not be put on an absolute scale so only energy diﬀerences have meaning. THE SECOND AND THIRD LAWS 95 .2) That is for every event the entropy of the universe increases. The mathematical statement of the second is for any spontaneous process T 4S ≥ q.23 THE SECOND AND THIRD LAWS Entropy forms the basis for the second and third laws of thermodynamics.

Use either the entropy as a measure of disorder concept of the number of conﬁgurations concept to predict whether or not the following spontaneous processes result in and increase or decease in entropy (a) melting of ice 96 THE SECOND AND THIRD LAWS .5) (23. X ° Sf.products − 4S ° = X ° Sf.reactants (23. but we can say it has an entropy of so-and-so.4) is the same as the sum of the 4S’s for the following reactions 2C6 H6 → 12C + 6H2 12C + 6H2 + 15O2 → 12CO2 + 6H2 O (23. Calculating Entropy Like we learned for enthalpy. That is 4S is solely determined by 4S = Sproducts − Sreactants regardless of how the reactants became the products.8) Group Work 1.6) (23. 4S for the reaction 2C6 H6 + 15O2 → 12CO2 + 6H2 O (23.So we can not say a glass of water as and energy of so-and-so. For example.7) We can also short cut the Hess’ law calculations by using the entropies of formation tables in Appendix L of the book. entropy is calculated in a similar manner.

Calculate 4rxn S ° for 1 1 1 NH3 + CO2 NH2 CONH2 + H2 O 2 2 2 using the entropies of formation given in the table below ° ¡ J ¢ substance Sf mol·K NH3 193 CO2 214 NH2 CONH2 174 H2 O 70 3. What is 4rxn S ° for NH3 + CO2 NH2 CONH2 + H2 O Homework Reading: Kotz and Treichel. 9. 11. 13. 17 THE SECOND AND THIRD LAWS 97 .4.(b) condensing of water vapor (c) the reaction between hydrogen and oxygen to form water (d) dissolution of NaCl in water 2. 15. 19. 7. 19.5 Problems: Chapter 19: 5.

98 THE SECOND AND THIRD LAWS .

for this course we are taking enthalpy to be heat energy (later in your career you will be more careful about this).24 GIBBS FREE ENERGY We have now dealt with the two processes that drive all the processes of nature including chemical reactions: Energy and Entropy. In most situations it is most convenient to use enthalpy as our energy. Now. it turns out that water is a liquid under these conditions. Nature wants to minimize enthalpy Nature also wants to maximize entropy Often these driving factors are in opposition and nature must adopt some compromise between minimizing enthalpy and maximizing energy. if only entropy was a factor. Since both factors contribute to the ﬁnal state of water. the water would be a vapor. Conversely. The Second Law If we consider the second law T 4S ≥ q. GIBBS FREE ENERGY 99 . For example consider water at room temperature and pressure. If only enthalpy was a factor than the water would be in the solid state.

We thus. If we rearrange this equation we get 4H − T 4S ≤ 0 The left hand side of this equation provides a very nice measure of spontaneity of a reaction. then 4H − T 4S is energy free to do work. if 4G is zero the process is at equilibrium. So if we consider 4H as the total energy available and T 4S as the tied up in randomizing the system.Hence. The deﬁnition of 4G also allows for another interpretation of Gibbs free energy. The 4H is the energy that the system can release or must take on for the process to occur The T 4S has units of energy and can be interpreted as the energy that is needed to produce the change in randomness associated 4S. If 4G is negative the process will proceed. Hence the term free energy Succinctly we say the Gibbs free energy is the energy available to do work. Gibbs Free Energy Notice how 4G captures natures great compromise between enthalpy and entropy. T 4S ≥ 4H. deﬁne what is called Gibbs free energy as the left hand side 4G = 4H − T 4S. but if 4G is positive the process will reverse. Finally. This energy is tied up and must be contained in the system. 100 GIBBS FREE ENERGY .

Consider the eﬀect of temperature on 4G. or both. or both. (a) melting of ice at room temperature (b) condensing of steam at room temperature (c) combustion of benzene into carbon dioxide and water.If 4G is negative then the free energy can be used to do work. Reactions can be energy driven. Consider the following spontaneous processes and state whether they are energy drive. (d) the rusting of iron 2. entropically driven. Group Work 1. entropically driven. If 4G is positive then work must be done on the system to get the process to go in the nonspontaneous direction. There are several ways 4G can be negative. (a) At what temperatures is enthalpy the more important factor? (b) At what temperatures is entropy the more importing factor? (c) A reaction that will not occur at 100K will occur at 500K what must be true? (d) A reaction that will occur at 100K will not occur at 500K what must be true? GIBBS FREE ENERGY 101 . If 4G is negative because the reaction is very exothermic (4H < 0) then we say the reaction is energy driven. If 4G is negative because the reaction is the entropy increase then we say the reaction is entropically driven.

4 H2 O −228.8 O2 0 CO2 −394. given ¡ kJ ¢ substance 4G° mol f C2 H5 OH −174.6 Problems: Chapter 19: 19. 29. 25. Like enthalpy and entropy. 31 102 GIBBS FREE ENERGY . Gibbs free energy can be calculated using Hess’ law or free energies of formation.3. Calculate 4G for C2 H5 OH + 3O2 2CO2 + 3H2 O. 23. 19.6 Homework Reading: Kotz and Treichel. 21. 27.

[i] = 1 M for all species) This relation is very important because we can know K by calculating 4rxn G° for any reaction using the free energies of formation. it can tell us which way the reaction will proceed to get to equilibrium. (25. The equilibrium constant is related to 4rxn G° by 4rxn G° = −RT ln K (25. 1 atm.2) We will call this equation the 4G equation and it is the most important equation in all of thermodynamics GIBBS FREE ENERGY AND EQUILIBRIUM 103 . So. unfortunately you will need to wait until later in your career to derive it from scratch. 4rxn G = 4rxn G° + RT ln Q. here we will simply state the relation. Indeed there is a connection. Thus there must be some connection between 4rxn G and both the equilibrium constant K and the reaction quotient Q. The 4rxn G for the reaction under any conditions is given by referencing to 4rxn G° and the reaction quotient.1) Remember 4rxn G° is the diﬀerence in free energies of the products and reactants under standard conditions (298 K.25 GIBBS FREE ENERGY AND EQUILIBRIUM We have seen that 4rxn G can tell us if we are at equilibrium and if we are not.

The diﬀerence between 4rxnG and 4rxnG° One point of confusion that often occurs is the distinction between 4rxn G and 4rxn G° . the value of 4rxn G° tells us whether or not the reaction is product favored or reactant favored. From positive 104 4rxn G° = −RT ln K = negative 4rxn G° = −RT ln K = positive <1 |{z} negative z}|{ >1 (25. the reaction would be product favored. Thus it is reactant favored. We said if K > 1. 4rxn G° is a constant for a given reaction that never changes over the course of the reaction. We see this because at standard condition all species present (both reactants and products) are 1 M. Conversely if K < 1. If 4rxn G° > 0 then under these standard conditions the system would move toward forming more reactants. Both 4rxn G and 4rxn G° tells us things about the character of the reaction. If 4rxn G° < 0 then under these standard conditions the system would move toward forming more products. it changes from negative to zero as the reaction proceeds towards equilibrium. Let’s see how this connects with the notion of product favored or reactant favored that we got from K. then the reaction is reactant favored. Thus it is product favored. 4rxn G is not constant.3) GIBBS FREE ENERGY AND EQUILIBRIUM . Since 4rxn G° is the diﬀerence in free energies of the products and reactants under standard conditions.

Initially there are no products and therefore Q = 0 and we have z}|{ 4rxn G = 4rxn G + RT ln 0 = −∞ ° −∞ (25. Then some products are formed but before we reach equilibrium Q < K.Turning to 4rxn G. initially there is a tremendous amount of thermodynamic force for the reaction to proceed. Thus z }| { <K 4rxn G = 4rxn G° + RT ln Q −RT ln K <K = −RT ln K + RT ln Q Q = RT ln = negative K |{z} | {z } negative <1 and the reaction will continue to proceed towards products. So if we consider the case where we mix reactants to perform a reaction. this tells us how the reaction will go under the current conditions of the reaction. GIBBS FREE ENERGY AND EQUILIBRIUM 105 . Thus z }| { >K 4rxn G = 4rxn G° + RT ln Q −RT ln K −RT ln K >K = −RT ln K + RT ln Q Q = RT ln = positive K |{z} | {z } positive >1 and the reaction will reverse to form reactants. At equilibrium Q = K and z }| { =K 4rxn G = 4rxn G° + RT ln Q = −RT ln K + RT ln K = 0 On the other side of equilibrium Q > K. even if very reactant favored.4) So regardless of what 4rxn G° .

Use the 4G equation to show these relationships. Earlier. 19. 2. LeChatelier’s principle is a consequence of the 4G equation. 43. 59. 34. Homework Reading: Kotz and Treichel. (Hint: the arguments will be similar to what we just discussed at the end of lecture. 65 106 GIBBS FREE ENERGY AND EQUILIBRIUM . 36.8 Problems: Chapter 19: 33. 19. Use the 4G equation to mathematically show LeChatelier’ss principle.7.Group Work 1. when we doubled the stoichiometry of a reaction we had to square the original K. Also when we turned a reaction around when had to take one over the original K. 35.

26 REVIEW OF CONCEPTS SURROUNDING GIBBS FREE ENERGY ∗ ∗ ∗ Worksheet ∗ ∗∗ REVIEW OF CONCEPTS SURROUNDING GIBBS FREE ENERGY107 .

108REVIEW OF CONCEPTS SURROUNDING GIBBS FREE ENERGY .

We ﬁrst need a few deﬁnitions. • When a species increases its oxidation number during a reaction it is oxidized. • When a species decreases its oxidation number during a reaction it is reduced. A general form for the oxidation—reduction reaction is Ahigh + Dlow → Alow + Dhigh . • A species which has a tendency to be reduced is called an oxidizing agent.1) Here a species A accepts an electron from a donor species D.2) It is more illustrative to write the net ionic equation by cancelling the spectator sulfate ion Cu2+ + Zn0 → Zn2+ + Cu0 . (27. (27. • A species which has a tendency to be oxidized is called a reducing agent because if it is oxidized the other reactant must be reduced. A is reduced since its oxidation number decreases and D is oxidized since its oxidation number increases For example an oxidation—reduction reaction between copper sulfate and zinc metal is written as CuSO4(aq) + Zn(s) → ZnSO4(aq) + Cu(s) .27 OXIDATION—REDUCTION REACTIONS I What distinguishes this type of reaction from the others is the fact that electrons are transferred during the reaction which results in a change in the oxidation numbers of the involved compounds. (s) (s) (aq) (aq) OXIDATION—REDUCTION REACTIONS I (27.3) 109 .

1. Homework Reading: Kotz and Treichel. Work on handout. 5. 3. Zinc acts as a reducing agent and copper acts as an oxidizing agent Balancing redox reactions It is important for you to become proﬁcient at balancing redox reactions. 2. There are three cases one needs to consider. Zinc is oxidized and copper is reduced. 4. 110 OXIDATION—REDUCTION REACTIONS I . 20. This requires practice.1 Problems: Chapter 20: 1. Examples 1. 6 *Note* these are due after the next lecture. The second is balancing redox reactions in acids and the third is balancing redox reactions in bases ∗∗∗ See Koltz & Treichel Section 20.Here we can clearly see that the oxidation number of the copper is reduced from 2+ to 0 whereas the oxidation number for zinc is increased from 0 to 2+. The ﬁrst is simply balancing redox reactions like the zinc—copper example above.2 and 3 ∗∗∗ Group Work 1. For this reaction two electrons are transferred from each zinc atom to each copper ion to create the zinc ion and the copper neutral atom.

Homework Reading: Kotz and Treichel. 6 OXIDATION—REDUCTION REACTIONS II 111 . 3. 5. 2. Work on handout. 20.1 Problems: Chapter 20: 1. 4.28 OXIDATION—REDUCTION REACTIONS II We will continue practicing balancing Redox reactions Group Work 1.

112 OXIDATION—REDUCTION REACTIONS II .

29 ELECTROCHEMICAL CELLS We now consider the example of the Daniell cell.1) In order to get usable energy from this reaction one must “separate” the half reactions Cu2+ (aq) + 2e− → Cu(s) and Zn(s) → Zn2+ + 2e− into two solutions as shown below (29. all of the chemical energy evolved is lost as heat and no work can be extracted. However. During the reaction electrons are transferred and the system moves to a lower energy state. The reaction Zn(s) + Cu2+ (aq) → Cu(s) + Zn2+ will occur spontaneously when mixed in a beaker.2) ELECTROCHEMICAL CELLS 113 .3) (29. (29.

• list components in phases from electrode to electrode • use a vertical line ( | ) to separate the phases • use a double vertical line ( || ) to indicate the salt bridge • start with the oxidation reaction on the left and then the reduction reaction on the right Applying the conventions to the Daniell cell we write Zn(s)|ZnSO4 (aq)||CuSO4 (aq)|Cu(s) to represent the cell. εcell = εright − εleft 114 (29. (29.5) ELECTROCHEMICAL CELLS .4) Standard Cell potentials The convention for the determining the potential of a cell is to take the REDUCTION potential for the “right” electrode minus the REDUCTION potential for the “left” electrode.Cell diagrams Conventions for writing down an electrochemical cell.

100 V Group Work 1. 20. 20. 23 ELECTROCHEMICAL CELLS 115 .337 V 1. This is how a battery recharger works. What voltage would need to be applied to a Daniel cell to “recharge” it. 11. 21. 15. 20. 13. pot. 19.3. 17. 20. How many electrons are transferred in the above reaction (be sure to consider the stoichiometry)? Homework Reading: Kotz and Treichel.2. 2.!! left (oxidation) right (reduction) cell reaction Zn(s) + Cu2+ (aq) → Cu(s) + Zn2+ Zn → Zn2+ + 2e− Cu2+ + 2e− → Cu −0.5 Problems: Chapter 20: 7.6) 3.For the Daniell cell we get: z }| { ε° 2 + |Zn Zn ε° 2 + |Cu Cu ε° cell red.763 V 0.4. To get a redox to go in reverse one must apply an opposing voltage in excess of the cell potential. What is the standard cell potential for 3Mg(s) + 2Al3+ (aq) → 2Al(s) + 3Mg2+ (29.

116 ELECTROCHEMICAL CELLS .

we can determine the free energy of the cell by 0 4rxn G = wmax = −nFεcell (30. −wmax = nFεcell where F = 96485 C/mol is Faraday’s constant. The Nernst equation then becomes z }| { RT ln K ⇒ −nFε° = −RT ln K 0 = ε° − nF ⇒ 4rxn G° = −RT ln K.30 THE NERNST EQUATION The cell potential allows one to determine the maximal work. (30. It is of interest to study the Nernst equation at equilibrium. At equilibrium Q = K and ε = 0 since the cell can do no work.2) As also have the 4G equation.3) [products] where Q = [reactants] is the reaction quotient (remember we are not at equilibrium) We can substitute 4rxn G = −nFεcell and 4rxn G° = −nFε° cell into the above equation to give the Nernst equation ε = ε° − RT ln Q nF (30. THE NERNST EQUATION 4rx n G° (30. That is.1) (30. the amount of work to move n moles of electrons though a potential εcell . −wmax the cell can produce. 4rxn G = 4rxn Gª + RT ln Q.5) 117 .4) The Nernst equation is one of the most important equations in all of electrochemistry since it provides a link to thermodynamics through Gibbs free energy via 4rxn G° = −nFε° from above. Once we know the maximal work for the cell.

M1 ) + e− ε° + |Na Na right (reduction) Na+ (aq.04 V 8. the diﬀerence in voltage from the standard potential is minimal. 2.100 M and the concentration of Zn2+ is 0.As we expected from earlier.100 ln 2 × 96485 0.M2 ) + e− → Na(Hg) ε° + |Na Na cell reaction 118 Na+ (aq. Example: What is ε for a Daniel cell at 300 K when the concentration of Cu2+ is 0. left (oxidation) Na(Hg) → Na+ (aq. Then we use the Nernst equation. These systems are called concentration cells. Consider Na(Hg)|NaCl(aq.M2 ) → Na+ (aq. Group Work 1.M1 )||NaCl(aq.001 The n = 2 because 2 electrons are transferred from the zinc to the copper during the reaction.M2 )|Na(Hg) (30. Explicitly derive the Nernst equation from the 4G equation.714 V 0V THE NERNST EQUATION .314 × 300 0. ε = 1.10 − = 1. What is K for the Daniels cell reaction? Is it product favored or reactant favored? 3.7) The double vertical lines ( || ) represent the salt bridge. We can also use a diﬀerences in concentrations between to half cells to do work.10 V.001 M? Zn(s) + Cu2+ (aq) → Cu(s) + Zn2+ (30.714 V −2. Notice that even though the concentrations diﬀer by a factor of 100.6) First we need ε° which we found last lecture to be 1.M1 ) ε° cell −2.

29. 20. 33. (a) What is the potential of a sodium concentration cell if the diﬀerence in concentration it a factor of 10? how about 100? how about 1000? (b) What is the 4G for the above cases? Homework Reading: Kotz and Treichel. 49 THE NERNST EQUATION 119 . 20. 20.6. 28.The Nernst equation becomes ε=0− RT [Na]1 RT [Na]1 ln ln =− n F [Na]2 F [Na]2 1↑ (30. 31. 26.7. 27. 37.8) So we see that if [Na]1 6= [Na]2 then a potential will develop. 45. 35.8 Problems: Chapter 20: 25. 39.

120 THE NERNST EQUATION .

31 REVIEW FOR EXAM 3 REVIEW FOR EXAM 3 121 .

Additional Material for Exam IV 122 REVIEW FOR EXAM 3 .

Electronegativity is a measure of the ability of an atom in a compound to attract electron density to itself.9 and 9.32 REVIEW OF MOLECULAR GEOMETRY We will be talking about the nature of intermolecular forces. ∗ ∗ ∗ See Figs. For covalent compounds the electron density is shared. Charge Distribution in Covalent Compounds We know that in ionic compounds electrons move entirely from one atom to another and the bond is formed due to the mutual attraction of the anion and the cation. 9. χ. These forces are determined and inﬂuenced by the three dimensional geometry of the molecule. However. 9.11 of Kotz&Treichel ∗ ∗∗ REVIEW OF MOLECULAR GEOMETRY 123 . it is not necessarily shared evenly between all the atoms in the compound. One way to characterize the charge distribution in compounds and polyatomic ions is to introduce the idea of electronegativity.8. As a result some atoms in the compound carry what are called partial charges. Thus we need to review the molecular geometry material from the ﬁrst semester.

The electronic geometry is the three dimensional structure that the electron density–either a bond or lone pair–adopts. • if the electronegativity exceeds 2.0 the bond is an ionic bond. Electronic Geometries • Linear: Two bonds or lone pairs • Trigonal planar: Three bonds or lone pairs • Tetrahedral: Four bonds or lone pairs 124 REVIEW OF MOLECULAR GEOMETRY . • if the electronegativities for the bonding pair diﬀer by less than 0. • if the electronegativity diﬀerence is between 0. The primary principle of the VSEPR model is that bonds and/or lone pairs of the valence electrons on each element of a compound repel each other and try to be as far away from one another as possible. A good approach to this is given by the valence shell electron repulsion (VSEPR) model. The atom with the higher electronegativity carries a partial negative charge while its partner with lower electron density carries a positive charge.5 then they essentially equally share the electrons. This type of bond is called a nonpolar covalent bond.0 then one atom attracts more electron density.For any given bonded pair the diﬀerence in electronegativities will determine just how equally the atoms share the bonding electrons. VSEPR Model Prior to discussing valence bond theory we need to learn something about the shapes of molecules. As a rule of thumb. Under the VSEPR model molecules can be classiﬁed according to there electronic geometry.5 and 2. This type of bond is called a polar covalent bond.

molecular in italic) • Linear — Linear: Two bonds. — Seesaw: Four bonds. two lone pairs. Three lone pairs. two lone pairs. no lone pairs. • Trigonal-bipyramidal — Trigonal-bipyramidal: Five bonds. — Square-planar: Four bonds. one lone pair. • Octahedral — Octahedral: Six bonds. no lone pairs. • Trigonal planar — Trigonal planar: Three bonds. no lone pairs. no lone pairs. one lone pair. two lone pairs. — Trigonal Pyramidal: Three bonds.• Trigonal-bipyramidal: Five bonds or lone pairs • Octahedral: Six bonds or lone pairs Once the molecule has been assigned its electronic geometry. — Bent: Two bonds. — Linear: Two bonds. • Tetrahedral — Tetrahedral: Four bonds. no lone pairs. REVIEW OF MOLECULAR GEOMETRY 125 . — Bent: Two bonds. it then gets assigned its molecular geometry. — Square-pryamidal: Five bonds. one lone pair. — T-shaped: Three bonds. Molecular Geometries (electronic geometry in bold. one lone pair.

Group Work 1. If all the polar bonds in a molecule cooperate in such a way that one side of the overall molecule is partially negative and the other side is partially positive then the molecule has a net dipole moment. Give the electronic and molecular geometries of the following molecules.Molecular Dipole Moments Polar covalent bonds with in molecule can potentially lead to a net dipole moment for the molecule. If all the polar bonds in a molecule cancel each other out then the molecule has no net dipole moment. Also indicate the direction of the dipole moment (a) NH3 (b) H2 CCl2 (c) BF3 126 REVIEW OF MOLECULAR GEOMETRY .

5. 11 REVIEW OF MOLECULAR GEOMETRY 127 .Homework Problems: Chapter 10: 1. 9. 3. 7.

128 REVIEW OF MOLECULAR GEOMETRY .

1) INTERMOLECULAR FORCES 129 . even for neutral molecules. is a measure of how the electron density of the molecules responds to an external electric ﬁeld.33 INTERMOLECULAR FORCES Polarizability and Induced Dipoles Last time we reminded ourselves of the molecular dipole moment. α. This distortion means that. An external electric ﬁeld causes the electron cloud of a molecule to become distorted. Unlike the permanent dipole moment that comes from appropriate molecular geometry. there can exits a dipole moment. this induced dipole is caused by the presence of the electric ﬁeld. Another equally important and somewhat related property of the molecule is its polarization. ε. The polarization. μ = αε (33. The dipole moment is important in determined intermolecular forces and the physical properties of substances.

The Coulombic Forces Ion—Ion: The force between two ions is the strongest molecular force and it has the longest interaction length. The force. 1 (33. F ∝ 1 r2 (33. r.3) F ∝ 3 r 130 INTERMOLECULAR FORCES . F . falls oﬀ relatively slowly with distance.2) Ion—dipole: This force is weaker than ion—ion interaction and it falls oﬀ with distance quicker.Figure 1 Figure 2 Intermolecular Forces There are several types of intermolecular forces that diﬀer in there make-up and in there interaction length.

The Van der Waals forces are weaker than the coulombic forces. an induced dipole can be created in the neighboring dipole. 1 (33. that dipole creates an electric ﬁeld that neighboring molecule feel. These forces are called Van der Waals forces. As you might expect these forces are weaker INTERMOLECULAR FORCES 131 . They also have a shorter interaction length dipole—dipole: The strongest of the Van der Waals forces with the longest interaction length. Consequently.Figure 3 Figure 4 The Van der Waals Forces Even when ions are not present one still sees intermolecular forces.4) F ∝ 4 r dipole—induced dipole: When a molecule has a permanent dipole.

having the form of F ∝ 1 r5 induced dipole—induced dipole (called Loudon or dispersive forces): One might think that there would be no interaction between molecules that have no permanent dipole. In fact there is an attractive force that does arise in these situations. The electron cloud and hence the polarization of the molecule is always ﬂuctuating. 132 INTERMOLECULAR FORCES . This induced dipole then strengthens the transient dipole by back induction. This random ﬂuctuation spontaneously creates a transient dipole moment which can then induce a dipole in a neighboring molecule.Figure 5 Figure 6 then dipole—dipole forces.

5. 13. 13. 6 INTERMOLECULAR FORCES 133 . 2. Give the principle type of intermolecular force for each of the following examples (a) NaCl in water (b) pure water (c) “Salt bridges” in proteins (d) methane dissolved in water (e) pure CCl4 Homework Reading: Kotz and Treichel. 3.2 Problems: Chapter 13: 1. F ∝ 1 r6 Group Work 1.The force is very weak and drops oﬀ very rapidly.1. 4.

134 INTERMOLECULAR FORCES .

Hydrogen bonding can occur in between some molecules that contain hydrogen. If a hydrogen is bonded to an oxygen. A hydrogen bond can be thought of as either an exceptionally strong physical interaction or a very weak chemical bond.34 HYDROGEN BONDING AND WATER Last time we discussed intermolecular forces. it can hydrogen bond to an oxygen. nitrogen or ﬂuorine atom can be hydrogen bond donors and acceptors. nitrogen or ﬂuorine atom in another molecule. Molecules that have an oxygen. Figure 1 HYDROGEN BONDING AND WATER 135 . nitrogen or ﬂuorine atom but no hydrogen attached to it can only be hydrogen bond acceptors. nitrogen or ﬂuorine atom in one molecule. Molecules that have a hydrogen bonded to an oxygen. There is one very important and special type of intermolecular force that we did not mention: hydrogen bonding.

Figure 2 Figure 3 136 HYDROGEN BONDING AND WATER .

13. 10. Homework Reading: Kotz and Treichel. 19. We don’t always appreciate how unique water is because we are so familiar with it. 21 HYDROGEN BONDING AND WATER 137 . 13. Group Work 1. 13.5 Problems: Chapter 13: 7. important and complicated substances know is water. Some of the unique properties of water are • An abnormally high melting point • An abnormally high boiling point • The fact that ice ﬂoats • The Grotthuss mechanism • A high heat capacity • A high dielectric constant.Water One of the most interesting.3. 17. 13.4. Restate in your own words why hydrogen bonding is the reason for the unusual properties of water that we discussed in lecture. 9. 8. 11. 15. Almost all of the unique aspects of water are do to hydrogen bonds.

138 HYDROGEN BONDING AND WATER .

The solid—liquid line: • crossing the line from solid to liquid represents melting • crossing the line from liquid to solid represents freezing The gas—liquid line: • crossing the line from gas to liquid represents condensation • crossing the line from liquid to gas represents boiling The solid—gas line: • crossing the line from solid to gas represents sublimation • crossing the line from gas to solid represents deposition There are two special points on the phase diagram. ∗ ∗ ∗ HANDOUT ∗ ∗∗ The lines on the phase diagrams represent the precise temperatures and pressures where an equilibrium between two phases occurs. PHASE DIAGRAMS 139 . solid-gas line and gas-liquid line converge.35 PHASE DIAGRAMS The phase change behavior of a substance can be expressed conveniently with a pressure versus temperature graph called a phase diagram. • The triple point — The point where the solid-liquid line.

Suggest a way to go from a liquid to a gas without boiling. 35. • The critical point — The termination of the gas-liquid line. 33. 3.— The single value of temperature and pressure in which all three phases can co-exist. 13. 34. 37 140 PHASE DIAGRAMS .8 (skim). 13.7 (skim). 10 Problems: Chapter 13: 31. 13. How would the slope of the solid liquid line for the phase diagram for water compare to the generic one shown in the handout. Is there a way to go from a solid to a liquid without melting? Homework Reading: Kotz and Treichel. 13. Group Work 1. 36. 13.9.6 (skim). 2.

36 HOMOGENEOUS SOLUTIONS Homogeneous solutions are homogeneous mixtures of a solute in a solvent. There are several types of solutions based the nature of the solute • liquid-solid • liquid-liquid • liquid-gas Whether or not a particular solute dissolves in a particular solvent is determined by the intermolecular forces between the molecules. • Polar solutes dissolve more readily in polar solvents than in non-polar solvents • Non-polar solutes dissolve more readily in non-polar solvents than in polar solvents. Liquid-solid solutions The speciﬁc factors involved in the dissolution of a solid in a solvent are • breaking the lattice structure of the solid • the energy of interaction between the solute and solvent molecules HOMOGENEOUS SOLUTIONS 141 . The phrase “like dissolves like” captures the determining factors in the dissolution process.

• the energy of interaction between solvent molecules • the net entropy gain or loss due to dissolution.

**Liquid-liquid solutions
**

The speciﬁc factors involved in the mixing of liquids • The interaction energy between the solute molecules • The interaction energy between the solvent molecules • The interaction energy between a solvent molecule and a solute molecule • the net entropy gain or loss due to dissolution We can draw a phase diagram that captures the behavior of liquid-liquid mixtures. Rather than a pressure versus temperature graph we now use temperature versus mole fraction.

**Liquid-gas solutions
**

The speciﬁc factors involved in the mixing of liquids • The interaction energy between the gas molecule and the solvent molecule • The interaction energy between the solvent molecules • The entropy loss by dissolving the gas in the liquid. Notice that dissolving a gas in a liquid is entropically unfavorable. This means that gases dissolve better at low temperatures than at high temperatures.

142 HOMOGENEOUS SOLUTIONS

Figure 1

Group Work

1. An interesting thing happens when one put a salt like NaCl in to a miscible mixture of acetonitrile and water. The solution separates into a water-rich and acetonitrilerich phase. Why might this happen? 2. Related to the above there is a common “quick and dirty” technique for separating proteins from solutions called salting out. Here a salt is added to a protein—water solution to cause the protein to precipitate out as a solid. Why might this happen?

Homework

Reading: Kotz and Treichel, 14.1, 14.2 Problems: Chapter 14: 1, 3, 11, 13, 15, 17, 19

HOMOGENEOUS SOLUTIONS

143

144

HOMOGENEOUS SOLUTIONS

37 PROPERTIES OF SOLUTIONS We will now discuss some of the important properties of solutions. If we consider the case for a solution in a closed container with some headspace above the top of the liquid. there is a relationship between the make up of vapor phase and the solution. PROPERTIES OF SOLUTIONS 145 . Henry’s Law First of all there is a relationship between the partial pressure of the solute in the vapor phase and the solubility in the solution.

Raoult’s Law Another relationship between the vapor phase partial pressures and the solution exist for the solvent. Henry’s law is related to LeChatelier’s principle. we have solutesolution solutevapor If we where to increase the partial pressure of the solute in the vapor phase we would expect. If we look at Henry’s law. Pi is the partial pressure and ki is the Henry’s law constant. According to Raoult’s law the partial pressure of the solvent in the vapor phase above the solution is Ps = Xs Ps• . increasing the partial pressure makes the mole increase. 146 PROPERTIES OF SOLUTIONS . If we consider the equilibrium establishing in the closed container. We expect the mole fraction to go up. by LeChatelier’s principle.1) where Xi is the mole fraction of the solute.This relation is called Henry’s law and is Xi = ki Pi (37. that the reaction above would go in the reverse direction.

Positive deviation from Raoult’s lawNegative deviation from Raoult’s law Colligative properties Interestingly.where Ps• is the vapor pressure.e. PROPERTIES OF SOLUTIONS 147 . The properties that do this are called colligative properties. The physical interpretation of deviation from Raoult’s law is • positive deviation: the molecules prefer to be around themselves rather than other types of molecules. • no deviation: the molecules have no preference. certain physical properties always change the same way as a small amount of solute is added to a solvent. the partial pressure above pure solvent. i. there are speciﬁc interactions between particles. It does not require any kind of interaction among the constituent particle making up the solution. We will only discuss boiling point and freezing point. Since. • negative deviation: the molecules prefer to be around other types of molecules than themselves. in reality. real solutions generally deviate from Raoult’s law. Deviations from Raoult’s Law Raoult’s law is a purely statistical law.

the freezing point is lowered when a small amount of solute is added. This phenomenon is called boiling point elevation. This is called freezing point depression. as more solute is added the freezing point might begin to increase. As similar phenomenon occurs for freezing points. As one liquid moves from a high mole fraction to a low mole fraction. The initial boiling elevation. But. is independent of the nature of the solute. Again. Group Work 1. Eventually as more solute is added the boiling point might decrease depending on the nature of the solute. Sometimes Henry’s law is expressed in terms of concentration. now what would the units of Henry’s law constant be? 3. we would expect the liquid to ﬁrst obey Raoult’s law than to obey Henry’s law. What are the units on Henry’s law constant? 2. in this case. however. What must be true for about the relation between the vapor pressure and the Henry’s law constant for the liquid to obey both laws at all mole fractions? 148 PROPERTIES OF SOLUTIONS .When a small amount of solute is added to a solvent the boiling point is always initially elevated. For liquid—liquid mixtures it is not always clear what the solute is and what the solvent is. [i] = ki Pi .

23. 14. 39. 25. 51. 27.4 Problems: Chapter 14: 21.3. 33. 14. 41. 29. 47. 37.Homework Reading: Kotz and Treichel. 55 PROPERTIES OF SOLUTIONS 149 .

150 PROPERTIES OF SOLUTIONS .

38 REVIEW FOR FINAL EXAM REVIEW FOR FINAL EXAM 151 .

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