Chem 128 Notes

General Chemistry II Chemistry 128
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 Dierential Rate Laws The Reaction Rate . . . . . . . . . . . Rate Laws . . . . . . . . . . . . . . . . Elementary Reactions and Molecularity Group Work . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . .
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3 Determination of Rate Laws Dierential 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 . . . . . . . . . . . . . . . . . . . . . . . .

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 . . LeChateliers Principle . . Group Work . . . . . . . . Homework . . . . . . . . . 10 Review for Exam 1 11 Acids and Bases Brnstad 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 LeChateliers 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
15 The Common Ion Eect and Buers Buer Solutions . . . . . . . . . . . . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . .
61 62 64 65
16 More on Buers: The Henderson-Hasselbalch Equation 67 Group Work . . . . . . . . . . . . . . . . . . . . . . . 68 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 . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . 71 71 73 75 75 77 79 79 81 82 83 85 and Hess . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 87 88 90 91 91 93 93 94 94 95 96 96 97
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18 Titrations Part II Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 19 Solubility of Weak Electrolytes Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 20 Review for Exam 2 21 Review of the First Law, Enthalpy, Law The First Law of Thermodynamics . . . . Enthalpy . . . . . . . . . . . . . . . . . . . Hess Law . . . . . . . . . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . .
22 Entropy Microstates and Congurations . . . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . 23 The Second and Third Laws Calculating Entropy . . . . . . . . . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . .
CONTENTS
24 Gibbs Free Energy The Second Law . . Gibbs Free Energy . Group Work . . . . . Homework . . . . . .
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99 99 100 101 102
25 Gibbs Free Energy and Equilibrium 103 The dierence between 4rxn G and 4rxn G . . . . . 104 Group Work . . . . . . . . . . . . . . . . . . . . . . . 106 Homework . . . . . . . . . . . . . . . . . . . . . . . . 106 26 Review of Concepts Surrounding Gibbs Free Energy 107 27 OxidationReduction Reactions I 109 Balancing redox reactions . . . . . . . . . . . . . . . 110 Group Work . . . . . . . . . . . . . . . . . . . . . . . 110 Homework . . . . . . . . . . . . . . . . . . . . . . . . 110 28 OxidationReduction Reactions II 111 Group Work . . . . . . . . . . . . . . . . . . . . . . . 111 Homework . . . . . . . . . . . . . . . . . . . . . . . . 111 29 Electrochemical Cells Cell diagrams . . . . . . Standard Cell potentials Group Work . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 114 114 115 115
30 The Nernst Equation 117 Group Work . . . . . . . . . . . . . . . . . . . . . . . 118 Homework . . . . . . . . . . . . . . . . . . . . . . . . 119 31 Review for Exam 3 32 Review of Molecular Geometry Charge Distribution in Covalent Compounds VSEPR Model . . . . . . . . . . . . . . . . Molecular Dipole Moments . . . . . . . . . . Group Work . . . . . . . . . . . . . . . . . . Homework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 123 123 124 126 126 127
33 Intermolecular Forces 129 Polarizability and Induced Dipoles . . . . . . . . . . 129 Intermolecular Forces . . . . . . . . . . . . . . . . . . 130 Group Work . . . . . . . . . . . . . . . . . . . . . . . 133
4 CONTENTS
Homework . . . . . . . . . . . . . . . . . . . . . . . . 133 34 Hydrogen Bonding and Water . . . . . . . . . . . Group Work . . . . . . . . Homework . . . . . . . . . Water 135 . . . . . . . . . . . . . . . 137 . . . . . . . . . . . . . . . 137 . . . . . . . . . . . . . . . 137
35 Phase Diagrams 139 Group Work . . . . . . . . . . . . . . . . . . . . . . . 140 Homework . . . . . . . . . . . . . . . . . . . . . . . . 140 36 Homogeneous Solutions Liquid-solid solutions . . . . Liquid-liquid solutions . . . Liquid-gas solutions . . . . . Group Work . . . . . . . . . Homework . . . . . . . . . . 37 Properties of Solutions Henrys Law . . . . . . . . Raoults Law . . . . . . . Colligative properties . . . Group Work . . . . . . . . Homework . . . . . . . . . 38 Review for Final Exam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 141 142 142 143 143 145 145 146 147 148 149 151
CONTENTS
Material for Exam I
CONTENTS
CALCULUS IN A NUTSHELL
It is so much easier to talk about chemical kinetics if we have just a few ideas from calculus. The following is all the calculus we need to know.
Rates of Change
When considering chemical kinetics we will be interested in how fast a reaction proceeds. Experimentally this means we are in some way monitoring how the reaction is changing in time. We might be watching a reactant disappear as time goes on or we might be watching a reactant appear. We are measuring a rate of change of the reaction. Mathematically the rate of change is called a derivative. The concept of a derivative is one of two central concepts in calculus. Lets say we have some function that changes with time: f (t). We are interested in how it changes with time. We could consider two times and compare the function at each of these times. 4f = f (t2 ) f (t1 ). The rate of change might then be given by4t 4f , 4t
CALCULUS IN A NUTSHELL 7
where 4t = t2 t1 . Unfortunately this only works if the rate of change is constant during 4t. Obviously if 4t is big then this might not be the case. One of the central ideas of calculus is to consider the limit when 4t gets innitesimally small. We then write dt. If dt is suciently small then df dt is a good measure of the instantaneous rate of change. In calculus this is called the derivative of the function f with respect to t. Since the derivative is an instantaneous rate of change it holds for any function not just those that have a constant rate of change.
Slope
If we graph the function f then the derivative has a very nice graphical interpretation. The derivative at any time t is equal to the slope of the function at t.
The Anti-Derivative
As mentioned above, the derivative is one of two fundamental concepts in calculus. The other is the anti-derivative, which is more commonly called the integral. The integral is the answer to the question what function has this derivative?
Group Work
1. If a function is decreasing with time is its derivative positive or negative. 2. If a derivative is always zero what must be true about its anti-derivative? 3. Use a plot to show that 4f df = dt 4t only for a straight line. 4. If y = mx + b for a straight line, what is dy ? dx
Homework
Reading: Evaluation book, 14.1
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DIFFERENTIAL RATE LAWS
The Reaction Rate

Consider the reaction aA + bB cC + dD. (2.1)
We can monitor the rate of this reaction in a number of ways. We can watch either A or B disappear or we can watch either C or D appear. That is, we can monitor the derivative of the concentration of A, B, C or D with respect to time: d[I] , dt where [I] is the concentration of A, B, C or D. 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. 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. But, since the stoichiometry is xed for a given reaction, one can easily adjust the derivative of the concentration with respect to time to give a reaction rate, v, that is consistent regardless of which reactant or product is monitored. The rate (or velocity) of a reaction is v=
1 d[I] , I dt
(2.2)
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where I is the stoichiometric factor with the understanding that it is negative for reactants and positive for products. 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 (2.3)
Rate Laws
One of the primary goals of chemical kinetics is to determine how the rate of a reaction goes. That is to nd the rate law for the reaction. Kinetics is very much an empirical science that depends much more heavily on experimental results than on a strong theoretical foundation. As a result, rate laws must be experimentally determined rather than theoretically predicted. One very important and very common class of rate laws are ones in which the rate depends on the concentration of reactants present. Again considering the reaction aA + bB cC + dD, the rate laws of this type would be v = k [A]nA [B]nB , (2.4)
where nA and nB are constants, usually integers and k is the rate constant for the reaction. A dierential rate law for this reaction is then 1 d[A] = [A]nA [B]nB a dt (2.5)
The nA and nB powers on the concentrations are called orders of the reaction.
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Thus one would say this reaction is of order nA in A, of order nB in B, and of overall order nA + nB . 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 (2.6)
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 (2.7) be the overall reaction. 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] . 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, rate laws for overall reactions can not be determined by stoichiometry.
DIFFERENTIAL RATE LAWS 13
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. The rate determining step is the one in the series of elementary reactions that has the lowest rate constant k.
Group Work
1. Write the rate for the following reaction three times, each time monitoring a dierent reactant or product. 2H2 + O2 2H2 O 2. If the above reaction is elementary, write a dierential rate law for it.
Homework
Reading: Evaluation book, 14.2 Problems: Evaluation book Chapter 14: 3, 5, 9, 11, 12, 24, 26, 27, 28, 51, 63, 64
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3 DETERMINATION OF RATE LAWS
Concentrations [I] are measured not rates. To obtain the rate from the concentration we must examine how the concentration changes with time 1 d[I] I dt That is we must measure [I] as a function of time and nd the rate of change of this concentration curve. The rates of chemical reactions vary enormously from subseconds to years. Consequently no one experimental technique can be used. For slow reactions (hrs/days) almost any technique for measuring the concentration can be used. 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.
Dierential methods based on the rate law

Methods based directly on the rate law rely on the determination of the time derivative of the concentration. 1. Method of initial velocities for v = k[A]x [B]y rate laws.
DETERMINATION OF RATE LAWS 15
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. usually the experiment is run so the order can be easily determined by simple inspection. problems (a) if the concentration drops very sharply (b) if there is an induction period
2. 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 0.1 M 0.1 M 0.2 M [B]0 0.1 M 0.2 M 0.1 M
ood with, say, A so v kax [B]y
(3.1)
[A]95% 20 min 10 min 10 min
The data from run I gives an initial rate of vI = 0.05 0.1 M = 0.00025 M/min 20 min 0.05 0.1 M = 0.00050 M/min 10 min (3.2)
Likewise from runs II and III vII = and (3.3)
0.05 0.2 M = 0.00100 M/min 10 min Now, by comparison we can obtain the order. vIII =
(3.4)
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DETERMINATION OF RATE LAWS
Comparing runs I and II we see the rate has doubled. Thus doubling the concentration of B doubles the rate. Therefore the order dependence on [B] must be one. Comparing runs I and III we see the rate has doubled. Thus doubling the concentration of A quadruples the rate. Therefore the order dependence on [A] must be two. So nally we can write the rate law as v = k [A]2 [B]. (3.5)
Notice the orders have nothing to do with the stoichiometric factors. They are equal to the stoichiometric factors only for elementary reactions. Example: Method of Isolation Again consider the reaction aA + bB cC and the following experimental data. Run [A]0 [B]0 obs. order I 1.00 0.01 1 II 0.01 1.00 2 From run I we see that the reaction depends on [B] to the rst power From run II we see that the reaction depends on [A] to the second power. Therefore the overall rate law is v = k [A]2 [B].
DETERMINATION OF RATE LAWS 17
(3.6)
Group Work
1. Sometimes the initial rate data is presented slightly differently. Consider the reaction aA + bB cC and the data Run I II II [A]0 0.1 M 0.1 M 0.2 M [B]0 0.1 M 0.2 M 0.1 M [A]10 min 0.095 M 0.090 M 0.180 M
What is the overall rate law? 2. Consider the reaction aA + bB + cC dD and the following data Run I II III IV [A]0 0.1 0.1 0.1 0.2 [B]0 0.1 0.1 0.2 0.1 [C]0 0.1 0.2 0.1 0.1 [A]95% 100 sec 50 sec 100 sec 100 sec
what is the overall rate law? 3. Explain in your own words the strategy of the method of isolation.
Homework
Reading: Evaluation book, 14.3 Problems: Evaluation book Chapter 14: 14, 18, 48, 49, 53, 54, 55, 56
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DETERMINATION OF RATE LAWS
INTEGRATED RATE LAWS
The previous lecture dealt with dierential rate laws look directly at the rate law which is a dierential equation. The dierential equation is not solved. We now solve the dierential equations to yield what are called the integrated rate law. The dierential equations (rate law) and their solutions (integrated rate law) are simply listed here for a few rate laws. type 1st order 2nd order nth orderb) enyzme
a) 1 i 1 i 1 i 1 i
rate lawa)
d[I] dt d[I] dt d[I] dt d[I] dt
integrated rate lawa) [I] = [I0 ]e i kt 1 = [I10 ] i kt [I] 1 = [I0 ]1 (n 1) i kt n1 [I]n1 [I0 ] km ln [I] + ([I0 ] [I]) = 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 i is the stoichiometric factor for [I] (n.b., i is a negative number). b) The order need not be an integer. For example n = 3/2 is a three-halves order rate law.
Linearizing the integrated rate laws

We see from the table above that the integrated rate law for rst order behavior is [I] = [I0 ]e i kt , which is of the form of an exponential. (4.1)
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With a computer and a program like Microsoft Excel it is easy to work with the data as is. Sometimes, however, it is convenient to cast the data into linear form. For a rst order reaction this is done by taking the natural log of the integrated rate law ln[I] = ln [I0 ]e i kt (4.2) i kt ln[I] = ln[I0 ] + ln e ln[I] = i kt + ln[I0 ]. |{z} | {z } |{z}
y mx b
So, by plotting the natural log of experimental data versus time, rst order reactions will appear as straight lines with a slope equal to i k.
The second and higher order integrated rate laws given in the table about are already in linearized 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 i k: 1 1 = i kt + . (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. Instead one uses an observed rate constant, kobs . Thus overall reactions that appear to be rst order follow the linearized integrated rate law, ln[I] = kobs t + ln[I0 ] and second order reactions go as 1 1 = kobs t + [I] [I0 ]
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(4.4)
(4.5)
Group Work
1. Identify y, m, x and b in the linearized nth order integrated rate law. 2. We have talked about rst and second order reactions. If we consider a zeroth order rate law, we must solve the dierential equation 1 d[I] = k[I]0 = k i dt d[I] = i k. dt From what we learned in the rst lecture, we can solve this equation. The equation is asking us to nd the function [I] that has a constant derivative that is equal to i k. (a) Given the slope interpretation of the derivative, 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, equal to the initial concentration) at t = 0
Homework
Reading: Evaluation book, 14.4, 14,5 Problems: Evaluation book Chapter 14: 10, 16, 20, 58, 59, 61, 62
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22
THE ARRHENIOUS EQUATION
Temperature Dependence of the Rate Constant
We have learned that kinetics is an empirical science. That is, it is based more on experiment than on theory. One experimental observations is that the rate of a reaction generally increases as the temperature increases. In other words, the rate constant gets bigger with increasing temperature. An empirical rate constant that often captures the correct temperature dependence was proposed by Arrhenious: k = Ae RT
Ea
(5.1)
where Ea is the Arrhenious activation energy and A is a constant called the frequency factor. Notice that if one takes the natural log of the Arrhenious equation one has ln k = ln A Ea . RT (5.2)
1 If ln k is plotted versus T we get a straight line whose slope is Ea and intercept is ln A. R
So one needs to know the rate constant at least two temperatures to determine the Arrhenious parameters.
THE ARRHENIOUS EQUATION 23
Application of the Arrhenious Equation

The best way to get a feel for the Arrhenious equation is to work a few examples. Example 1: A reaction is found to go 1.5 times faster at 400 K than at 300 K. What is the Arrhenious activation energy for this reaction? The reaction goes 1.5 times faster means k400 = 1.5k300 . So Ae 400R = 1.5Ae 300R Ea Ea e 400R = 1.5e 300R . Taking the natural log of both sides gives Solving for Ea gives Ea Ea = ln 1.5 300R 400R 1 1 = ln 1.5 Ea 300R 400R ln 1.5 Ea = 1 1 400R 300R Ea = 4045 J/mol Example 2: The Arrhenious activation energy is 50.50 kJ/mol for some reaction. How much faster will the reaction go at 298 K than at 273 K? We want to nd the ratio
k298 . k273
50500 Ea Ea
Ea Ea = ln 1.5 . 400R 300R
Thus,
1 1 k298 Ae 298R 50500( 273R 298R ) = 50500 = e k273 Ae 273R = 6.47.
So the reaction goes 6.47 times faster at 298 K than at 273 K.

24 THE ARRHENIOUS EQUATION
Catalysts
The Arrhenious activation energy creates a barrier for reactions to proceed. The higher the energy barrier the slower the reaction will go. We have learned that one way to speed up a reaction is to heat it. Sometimes heating is not desirable. There is an additional method for lowering the activation energy barrier. 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 (5.3)
Group Work
1. A certain reaction goes twice as fast at 1000 K than at 300 K. What is the Arrhenious activation energy? 2. A certain reaction has an activation energy of 34 kJ/mol. How much faster will the reaction go at 300 K than at 100 K? 3. Reaction I has a large Arrhenious activation energy and reaction II has a small one. Both reaction I and reaction II take the same amount of time to reach completion at 298 K. 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
Homework
Reading: Evaluation book, 14.7, 14.8 Problems: Evaluation book Chapter 14: 131, 33, 37, 39, 41, 68,. 69, 70, 71, 74, 75
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THE ARRHENIOUS EQUATION
KINETICS AND EQUILIBRIUM
Our next topic will be chemical equilibrium. There is a relation between kinetics and equilibrium. Last semester and up to this point we have been talking about reactions that go all the way to completion. Most reactions, however, do not go to completion but reach an equilibrium with a certain amount of reactants still left over. We can understand equilibrium from the standpoint of kinetics by not only considering the forward reaction, aA + aB cC + dD
k kf
(6.1)
but also the reverse reaction,
These can be written as one reaction with a double arrow, aA + aB cC + dD.

kr kf
r cC + dD aA + bB.
(6.2)
(6.3)
The forward reaction rate depends on the concentration of reactants, (6.4) vf = kf [A]nA [B]nB , while the rate of the backwards reaction depends on the concentration of products vr = kr [C]nC [D]nD . (6.5) Equilibrium occurs when the reaction rate in both the forward and reverse directions are equal, vf = vr , or kf [A]nA [B]nB = kr [C]nC [D]nD [C]nC [D]nD kf = =K kr [A]nA [B]nB
(6.6) (6.7)
27
Group Work
1. Does the ratio of rate constants tell us how fast the reaction reaches equilibrium. Hint: consider the units.
Homework
Problems: Evaluation book Chapter 14: 78, 80, 81, 82, 84
28
EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT
Last lecture we began to consider the fact that usually reactions do not go all the way to completion, but rather, they reach an equilibrium. The topic of equilibrium is of essential importance to general chemistry and will be discussed for nearly the rest of the semester. The rst topic in equilibrium we will discuss is the equilibrium constant
The Equilibrium Constant

We already sort of saw the equilibrium constant last time. For a given reaction, aA + bB cC + dD, the equilibrium constant is dened as K= [C]c [D]d [A]a [B]b .
Notice here, unlike kinetics, we can rely on the stoichiometry of the reaction to give us the proper K values. The equilibrium constant tells us how much of each of the reactants and products are present after the reaction reaches equilibrium.
EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT 29
Because of this, K provides a criteria for labeling a reaction as product favored or reactant favored. Product favored reactions are those in which there are more products around than reactants at equilibrium. Thus K > 1 for product favored reactions. Reactant favored reactions are those in which there are more reactants around than products at equilibrium. Thus K < 1 for reactant favored reactions. Sometimes concentrations are not the most convenient value to use for the equilibrium constant. One example are gas phase reactions. Here partial pressures are used in place of concentrations, KP =
c d PC PD . a b PA PB
Another case where one does not use concentration is when referring to the solvent. Consider the reaction aA + bB cC + H2 O that takes place in water. Here water is the product and the solvent. In these cases K= [C]c [A]a [B]b
The concentration of water is not used. One also does this when pure substances are used as reactants or produces as products. Consider aA(aq) + bB(s) cC(aq) + dD(aq) . Here [C]c [D]d , K= [A]a
30 EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT
Group Work
1. 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, 16.1, 16.2, 16.3 Problems: Chapter 16: 1, 3, 5, 7, 8, 9, 10, 11
31
32
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. These calculations can be aided through the used of an ICE chart. The I stands for initial concentration, the C stands for change in concentration, and the E stands for equilibrium concentration. Use of ICE charts are best illustrated by way of examples. Example 1: Consider the reaction A(aq) + 2B(aq) C(aq) , (8.1)
where K = 1.23 102 . Initial concentrations of A and B are each 1.00 M. Determine the concentration of reactants and products at equilibrium. We set-up our ICE chart A B C I 1.00 1.00 0 x 2x x C E 1.00 x 1.00 2x x We now use the equilibrium constant, K = 1.23 102 = x (1.00 x) (1.00 2x)2 (8.2)
We can rearrange this to give 492x3 984x2 + 616x 123 = 0 (8.3)
Unfortunately we are now faced with a cubic equation to solve.

ICE CHARTS 33
This is hard to solve algebraically but you can use your calculators to get three solutions: x = 0.459, x = 0.550, x = 0.992. Only one of these solutions can be the real answer. We can gure that out by inspection. Since the nal concentration of B is 1.00 2x, only the x = 0.459 solution makes sense. The other solutions give a negative concentration for B. Thus the nal equilibrium conditions are [A] = 1.00 0.459 = 0.541 M [B] = 1.00 2 0.459 = 0.082 M [C] = 0.459 M Example 2: Consider the reaction A(g) B(g) + C(g) , (8.5) (8.4)
where Kp = 4.23 101 . The initial partial pressure of A is 0.333 atm. Determine the concentration of reactants and products at equilibrium. First we set-up the ICE chart A B I 0.333 0 C x x E 0.333 x x The equilibrium equation is Kp = 4.23 101 = This can be rearranged into x2 + 0.423x 0.141 = 0 (8.7) (x) (x) (0.333 x) (8.6) C 0 x x
This is a quadratic equation so we can easily get the solutions via the quadratic formula, bx ax2 + + c = 0 b b2 4ac x = 2a
34
(8.8)
ICE CHARTS
For this example, p 0.4232 4 (0.141) x = 2 x = 0.642, x = 0.219. 0.423
(8.9)
Again, we need to determine the real solution by inspection. A negative x does not make physical sense so x = 0.219 is our solution. The nal equilibrium conditions are PA = 0.333 0.219 = 0.114 atm PB = 0.219 atm PC = 0.219 atm
(8.10)
Group Work
1. Normally when we use the stoichiometry of a reaction we must compare moles, but the ICE chart uses concentration directly. Why does this work? Can you think of situations where it would not work? 2. Use the ideal gas law to derive the relationship between K and KP : KP = K(RT )4n .
Homework
Reading: Kotz and Treichel, 16.4, 16.5 Problems: Chapter 16: 13, 14, 15, 17, 18, 19, 21, 23
ICE CHARTS
35
36
ICE CHARTS
9 THE REACTION QUOTIENT AND LECHATELIERS PRINCIPLE
We have seen that the equilibrium constant is an important quantity. It turns out that one can extend the denition of the equilibrium constant to non-equilibrium situations.
The Reaction Quotient

Under non-equilibrium situations the ratio of the concentration (or partial pressures) of products to reactants is called the reaction quotient, [products] Q= . (9.1) [reactants] So, for the reaction, aA + bB cC + dD, the reaction quotient is Q= [C]c [D]d [A]a [B]b . (9.3) (9.2)
The reaction quotient applies to the current situation of the reaction and thus changes over the course of the reaction. Clearly, at equilibrium Q = K. Beyond that, however, if Q < K the reaction will proceed in the forward direction (make more products). And, if Q > K the reaction will proceed in the reverse direction (make more reactants).
THE REACTION QUOTIENT AND LECHATELIERS PRINCIPLE 37
LeChateliers Principle
One of the most important concepts in equilibrium is LeChateliers principle which describe how systems behave when they are taken out of equilibrium LeChateliers 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 eect of that change. Consider the reaction aA + bB cC + dD, at equilibrium. Now consider adding more reactant A or B. Takes the system out of equilibrium to the reactant side of the reaction. LeChateliers principle says the system will respond by making more product. Conversely if more product is added the system is shifted out of equilibrium to the product side. LeChateliers principle says the system will respond by going in reverse to make more reactant. We can capture LeChateliers principle mathematically by considering the reaction quotient. At equilibrium Q = K. If reactant is added then the denominator of Q gets bigger and Q < K. This Q < K condition says that the reaction will proceed forward. Similarly, if product is added the system the numerator of Q gets better and Q > K. (9.4)
This Q > K condition says that the reaction will go in reverse. Temperature can also play a role. If a reaction is exothermic we can think of heat as one of the products. Conversely if a reaction is endothermic we can think of heat as one of the reactants. 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, 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. Now, however, it is the equilibrium constant that changes with temperature. For endothermic reactions K as T and for exothermic reactions K as T . So, if the system is at equilibrium at one temperature K = Q. If the temperature changes then K changes while Q stays the same. Consequently, K 6= Q and the system will adjust accordingly.
Group Work
1. Lets say an important drug was produced in a reaction A + B Drug. but the equilibrium constant was small. The reactants A and B are both very expensive. Suggest a way to use
THE REACTION QUOTIENT AND LECHATELIERS PRINCIPLE 39
LeChateliers principle to get the most drug for the least amount of reactant. 2. Consider the above problem but now A is very expensive but B is very cheap. Also assume that your suggestion from above was dicult to do in the lab for this drug. Use LeChateliers principle to get the most amount of drug for the least expense. 3. How would LeChateliers principle apply to gas phase reaction where the pressure is changed?
Homework
Reading: Kotz and Treichel, 16.7, 16.8 Problems: Chapter 16: 25, 26, 27, 28, 41, 43, 49
10
REVIEW FOR EXAM 1
REVIEW FOR EXAM 1
41
Material for Exam II
42
REVIEW FOR EXAM 1
11
ACIDS AND BASES
We are familiar with acids and bases and their reactions from last semester. We will spend the next few lectures looking at acidbase reactions in the context of equilibrium
Brnstad Acids and Bases

Our rst denition of an acid or base is what called the BrnstadLowry concept of an acid or base. A Brnstad acid is any compound that can donate a proton A Brnstad base is any compound that can accept a proton Brnstad acids that can donate one proton, like HCl are called monoprotic acids. Brnstad acids that can donate more than one proton, like H2 SO4 are called polyprotic acids.
Conjugate Acid-Base Pairs

Within the Brnstad-Lowry concept of an acid or base, an acid base reaction involves the transfer of a proton from the acid to the base, HA + B A + HB (11.1) Here HA in it is the acid and B is the base.
ACIDS AND BASES 43
We could write the reaction in reverse, A + HB HA + B Now A is the base and HB is the acid. So within the reaction HA and A form a so-called conjugate acid-base pair. Likewise B and HB form a conjugate pair. For conjugate acid base pairs, the stronger one partner is, the weaker the other partner is. So a strong acid has a corresponding weak conjugate base and a weak acid has a strong conjugate base. For polyprotic acids we must consider each proton donation separately, H2 A + B2 HA + HB A2 +H2 B. Here the conjugate pairs are H2 A HA HB H2 B HA A2 B2 HB (11.2)
Group Work
1. Give the conjugate partner for (a) HNO3 (b) H2 CO3 (c) HCO 3 (d) NH3 (e) H2 O 2. Identify the conjugate acid-base pairs in the following reactions
44 ACIDS AND BASES
(a) (b)
CH3 CO2 H + NH3 CH3 CO + NH+ 2 4 H2 S + H2 O HS + H3 O+
3. 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. The simplest amino acid is glycine, H2 NCHCOOH. The nitrogen end can act like a Brnstad base by accepting another proton whereas the oxygen end can act like a Brnstad acid by giving up the proton attached to it. Write two separate reactions of glycine rst with a Brnstad acid and then with a Brnstad base.
Homework
Reading: Kotz and Treichel, 17.1, 17.2 Problems: Chapter 17: 1, 2, 3, 5, 6, 7
ACIDS AND BASES
45
46
ACIDS AND BASES
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. That is water under goes autoionization, 2H2 O(l) H3 O+ + OH (aq) (aq) (12.1)
Notice that we do not include the concentration of H2 O because it a considered a pure liquid. At standard conditions of 25 C, Kw = 1.0 1014 = H3 O+ OH .
We can write the equilibrium constant for this reaction as K = Kw = H3 O+ OH . (12.2)
If we now consider the addition of an Brnstad acid to water, we see that the H3 O+ goes up: Q > Kw .
By the symmetry of the reaction, two water molecules creates one H3 O+ and one OH , then for pure water H3 O+ = OH = 1.0 107 .
By LeChateliers principle, the autoionization is driven backwards, H3 O+ + OH 2H2 O(l) , (aq) (aq) The only source of OH is from the original water. Therefore the concentration of OH goes down. More precisely the autoionization reaction is driven backwards until H3 O+ OH = Kw . A similar situation arrises for addition of a Brnstad base.
WATER AND PH
47
The pH Scale
The inverse relationship between H3 O+ and OH is seen in the pH scale. Consider taking the negative log of Kw , log Kw = log 1.0 1014 = 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, determination of pH is relatively easy based on the LeChatelier arguments above. Example 1: What is the pH of a 2.3103 M solution of HCl. Since HCl is a strong acid, it fully dissociates to produce a 2.3 103 M solution of H3 O+ . The pH is simply pH = log 2.3 103 = 2.63
Example 2: What is the pH of a 2.3 103 M solution of NaOH. Since NaOH is a strong base, it fully dissociates to produce a 2.3 103 M solution of H3 O+ . The pOH is pOH = log 2.3 103 = 2.63 pH = 14 2.63 = 11.36
48 WATER AND PH
From the 14 =pH + pOH relationship
Group Work
1. Identify the conjugate pairs in the autoionzation reaction for water. 2. Considering the Kw data for dierent temperatures given in the table below
C Kw 10 0.29 1014 25 1.00 1014 50 5.48 1014 (a) Is the autoionization reaction exothermic or endothermic? (b) What is the pH range at 50 C? 3. What is the pH of a 4.56 102 M solution of HNO3 ? 4. What is the pH of a 7.89 1010 M solution of KOH? Does this answer make any sense? If not, why not?
Homework
Reading: Kotz and Treichel, 17.3, Problems: Chapter 17: 9, 10, 11, 12, 13, 14
WATER AND PH
49
50
WATER AND PH
13
ACID AND BASE EQUILIBRIA
Up until now we have been considering strong acids and bases in which the acid or base fully dissociates. For weak acids and bases we must set-up an equilibrium expression. For a weak acid equilibrium reaction, HA H+ + A , the equilibrium expression is + A H Ka = [HA] where Ka is called the acid dissociation constant. The larger the Ka the stronger the acid Likewise for a weak base equilibrium reaction, BOH B+ + OH , the equilibrium expression is + B OH Kb = [BOH] where Kb is called the base dissociation constant. There is a relationship between Ka and Kb for conjugate acid base pairs. The relationship is Ka Kb = Kw . (13.5) (13.3) (13.2) (13.1)
(13.4)
If the acid (or base) is polyprotic then there are multiple Ka values (Ka1 , Ka2 , etc.) for each of the dissociation reactions.
ACID AND BASE EQUILIBRIA 51
Usually Ka1 Ka2 Ka3 . For polyprotic acids (or bases) we must consider separate equilibrium reactions H2 A H+ + HA HA H+ + A2 where, for this case, Ka1 Ka2 + HA H , = [H2 A] + 2 A H = HA (13.7) (13.6)
Example 1: Calculate the pH of a 0.012 M solution of niacin (HC 6 H 4 NO 2 ). The Ka = 1.4 105 . We rst write the appropriate equilibrium reaction HC6 H4 NO2 H+ + C6 H4 NO . 2 Next we setup an ICE chart, [HC6 H4 NO2 ] I 0.012 C x E 0.012 x From Ka we get the equation, Ka = 1.4 105 = (x) (x) (0.012 x) (13.9) + H C6 H4 NO 2 0 0 . x x x x (13.8)
Therefore the
Rearranging and solving for x using the quadratic formula we get x = H+ = 4.1 105 . (13.10) pH = log 4.1 105 = 3.39 (13.11)
Example 2: What is the pH of a 0.10 M solution of vitamin C (H 2 C 6 H 6 O 6 ). The Ka1 = 7.9 105 and Ka2 = 1.6 1012 . In general this problem is more complicated because of the two Ka values. However, as will often be the case Ka1 Ka2 so Ka1 alone will determine the pH.
52 ACID AND BASE EQUILIBRIA
Like above we rst write that appropriate reaction, H2 C6 H6 O6 H+ + HC6 H6 O 6 and produce an ICE chart [H2 C6 H6 O6 ] I 0.10 C x E 0.10 x The Ka1 equation gives Ka1 = 7.9 105 = (x) (x) . (0.10 x) + H HC6 H6 O 6 0 0 x x x x
Therefore the
Rearranging and using the quadratic formula gives x = H+ = 0.0028. pH = log (0.0028) = 2.55
Example 3: Calculate the concentration of C 6 H 6 O 2 for the 6 case of example 2. 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. The ICE chart is + HC6 H6 O H C6 H6 O2 6 6 I 0.0028 0 0 . C y y y y y E 0.0028 y Utilizing Ka2 = 1.6 1012 = and solving to get (y) (y) (0.0028 y)
y = C6 H6 O2 = 6.7 108 6
ACID AND BASE EQUILIBRIA 53
Group Work
1. What is the pKa for niacin and what are the pKa1 and pK2 values for vitamin C? 2. What is the pH of a 0.10 M solution of the base, hydrazine (N2 H2 ). The Kb = 1.7 106 . 3. What is the equilibrium concentration of SO2 if one ini3 tially prepares a 0.100 M solution of H2 SO3 ? The Ka values are: Ka1 = 1.3 102 and Ka2 = 6.3 108 .
Homework
Reading: Kotz and Treichel, 17.4 Problems: Chapter 17: 15, 17, 19, 21, 23, 25, 27, 29, 31
54
ACID AND BASE EQUILIBRIA
14 REACTIONS WITH WEAK ACIDS AND WEAK BASES
We have learned how to determine the pH of a weak acid or weak base solution. We will now extend that to include calculating the pH after a acidbase reaction.
Reaction Between a Monoprotic Weak Acid and a Strong Base

We rst consider a reaction between a weak monoprotic weak acid with a strong base. We will take the reactants to be present in stoichiometric ratios. We will not consider limiting reagent cases until later. Since this is a reaction between a weak base and a strong base we would expect the nal pH to be basic. Example: What is the nal pH if 25 ml of a 0.10 M niacin (HC 6 H 4 NO 2 ) is reacted with 25 ml of 0.10M NaOH. For niacin the Ka = 1.4 105 . We rst write a balanced reaction, HC6 H4 NO2 + NaOH NaC6 H4 NO2 + H2 O. It is convenient to express the net ionic equation, HC6 H4 NO2 + OH C6 H4 NO + H2 O. 2 (14.2) (14.1)
We know that sodium hydroxide is a strong base so it fully dissociates to produce OH .

REACTIONS WITH WEAK ACIDS AND WEAK BASES 55
All of the OH reacts with the H+ from niacin. Now this leaves only C6 H4 NO , 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 . 2 The Kb for this reaction is obtain from the Ka for niacin and Kw , Kw = 7.14 1010 . (14.3) Kb = Ka We will need to setup and ICE chart but rst we must determine the concentration of C6 H4 NO . 2 To do this we see, 0.025 L HC6 H4 NO2 0.10 mol C6 H4 NO 0.10 mol HC6 H4 NO2 2 L 0.10 mol HC6 H4 NO2
= 0.0025 mol C6 H4 NO 2 But we also had 25 mL from the NaOH solution so the total volume is now 50 mL thus, 0.0025 mol C6 H4 NO 2 = 0.05 M C6 H4 NO C6 H4 NO2 = 2 0.050 L
Using this, the ICE chart is C6 H4 NO [HC6 H4 NO2 ] OH 2 I 0.05 0 0 . C x x x E 0.05 x x x So, we have Kb = 7.14 1010 = (x) (x) (0.05 x)
Hence,
Rearranging and using the quadratic formula we get x = [OH] = 5.97 106 . From this pOH = log 5.97 106 = 5.22. pH = 14 5.22 = 8.78.
The reaction between a weak base and a strong acid would be done in a similar manner.
56 REACTIONS WITH WEAK ACIDS AND WEAK BASES
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. Example: What is the nal pH of a reaction between 25 ml of a 0.10 M Vitamin C (H 2 C 6 H 6 O 6 ) solution and 25 mL of a 0.20 M NaOH solution? The Ka1 = 7.9 105 and Ka2 = 1.6 1012 . 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 . The concentration of C6 H6 O2 is 6 6 0.025 L H2 C6 H6 O6 0.10 mol H2 C6 H6 O6 0.10 mol C6 H6 O2 6 L 0.10 mol H2 C6 H6 O6
= 0.0025 mol C6 H6 O2 6 The total volume after the reaction is 50 mL so, 0.0025 mol C6 H6 O2 6 C6 H6 O2 = = 0.05 M C6 H6 O2 . 6 6 0.050 L Kw = 1.2 1010 Ka1 Kw = = 6.3 103 . Ka2
We need to now consider the weak base equilibrium of C6 H6 O2 . 6 The Kb s are obtained from the Ka s, Kb1 = Kb2
Since Kb2 Kb1 , 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 0.05 0 0 . C x x x E 0.05 x x x
REACTIONS WITH WEAK ACIDS AND WEAK BASES 57
From this Kb2 = 6.3 103 =
Rearranging and using the quadratic formula we get x = OH = 0.015 and pOH = log (0.015) = 1.82. So, nally, pH = 14 1.82 = 12.18
(x) (x) (0.05 x)
Reaction Between a Weak Acid and a Weak Base

The reaction between a weak acid and a weak base requires a dierent strategy since we can not exploit the full dissociation of the strong acid or base as we did above. We can perform this calculation by using Hess law from last semester. Example: What are the nal concentrations of products if 25 ml of a 0.10 M niacin solution ( Ka = 1.4 105 ) is reacted with 25 ml of a 0.10 M NH 3 solution ( Kb = 1.8 105 )? As before, we start with a balanced equation HC6 H4 NO2 + NH3 C6 H4 NO + NH+ . 2 4 We now use Hess law to write HC6 H4 NO2 H+ + C6 H4 NO Ka = 1.4 105 2 NH3 + H2 O NH+ + OH Kb = 1.8 105 4 H+ + OH H2 O 1/Kw = 1.0 10+14 This gives the original reaction and the equilibrium constant for this reaction is K= Ka Kb = 2.5 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.
58
REACTIONS WITH WEAK ACIDS AND WEAK BASES
We can then setup an ICE chart as + [HC6 H4 NO2 ] [NH3 ] C6 H4 NO NH4 2 I 0.05 0.05 0 0 C x x x x E 0.05 x 0.05 x x x Thus, K = 2.5 10+4 = (x) (x) (0.05 x) (0.05 x) = = = = 0.0004 0.0004 0.0496 0.0496 M M M M
Rearranging a solving for x gives x = 0.0496. So, [HC6 H4 NO2 ] [NH3 ] C6 H4 NO 2 NH+ 4
Work Group
1. What is the nal pH if 25 ml of a 0.10 M ammonia solution is reacted with 25 ml of 0.10 M HCl? For ammonia the Kb = 1.8 105 .
Homework
Reading: Kotz and Treichel, 17.5, 17.6, 17.7, 17.8, 17.9 Problems: Chapter 17: 35, 37, 39, 41, 49, 61, 65, 67
59
60
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 .
By LeChateliers principle the reaction is shifted back towards the reactant. This shift in the equilibrium by LeChateliers principle is called the common ion eect. Example: How does the equilibrium shift when 10 mL of 0.010 M HCl is added to 25 mL of a 0.10 M niacin (HC 6 H 4 NO 2 ) solution ( Ka = 1.4 105 )? We rst need to determine the initial concentrations of niacin and the, common ion, H+ upon mixing. The new volume is 35 mL so, 0.025 L 0.1 mol HC6 H4 NO2 1 = 0.071 M HC6 H4 NO2 1L 0.035 L and 0.01 L 0.01 mol H+ 1 = 0.0028 M H+ 1L 0.035 L
We now can setup an ICE chart, + [HC6 H4 NO2 ] H C6 H4 NO 2 I 0.071 0.0028 0 . C x x x E 0.071 x 0.0028 + x x
THE COMMON ION EFFECT AND BUFFERS 61
With the Ka value we can get the equilibrium concentrations, Ka = 1.4 105 = (0.028 + x) (x) . (0.071 x) (15.1)
Rearranging and using the quadratic formula we get x = 3.2 104 . Hence [HC6 H4 NO2 ] = 0.071 3.2 104 = 0.071 + = 0.0028 3.2 104 = 0.0025 H C6 H4 NO = 3.2 104 2
Buer Solutions
An important application of the common ion eect occurs when the common ion is the conjugate pair to the original acid or base. These solutions are called pH buer solutions (or buers for short) and they have the valuable property that one can add a strong acid or base to a buer and not change the pH signicantly. The human body makes use of many buers to control the pH of the extra- and intra- cellular environments. Example, the acetate buer (part 1): Calculate the pH of an acetate buer 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 = 1.7 105 ). We rst 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+ = 2.8 105 . So, pH = log 2.8 105 = 4.55. Ka = 1.7 105 =
Example, the acetate buer (part 2): Calculate the pH if 10 ml of 0.01 M HCl is added to the above buer. Then compare this to the pH if the HCl was added to water. First we gure 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 1.7 105 = 0.063 M C2 H3 O = 0.038 + 1.7 105 = 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 = 1.7 105 =
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+ = 3.15 105 . So, pH = log 3.15 105 = 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 buer of the example in lecture. 2. What is the pH of an ammonium buer 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 buer calculations in a dierent way so that we can prepare a buer of a desired pH. Prepare 100 ml of a acetate buer with a pH of 4.25. (a) First use the pH nd 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
THE COMMON ION EFFECT AND BUFFERS
65
66
THE COMMON ION EFFECT AND BUFFERS
16
MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION
As we learned from the third group work question last time, it is important to be able to make buers of a desired pH. If we consider the Ka equation for a buer situation we have, + A H , (16.1) Ka = [HA] for the buer equilibrium, HA H+ + A . (16.2)
Now if we take of the negative log of the Ka equation, we get ! H+ A log Ka = log [HA] ! + A log Ka = log H log | {z } [HA] | {z } pKa pH ! A pKa = pH log [HA] Solving for pH gives the HendersonHasselbalch equation: ! A pH = pKa + log . [HA] We can use the HendersonHasselbalch equation to short-cut our buer calculations. Example 1: How would you make an acetate buer that has a pH of 4.25 ( Ka = 1.7 105 )?
MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION 67
The Using the HendersonHasselbalch equation we have ! C2 H3 O 2 4.25 = 4.77 + log [HC2 H3 O2 ] ! C2 H3 O 2 = 4.25 4.77 = 0.52 log [HC2 H3 O2 ] ! C2 H3 O 2 = 100.52 = 0.30 [HC2 H3 O2 ] This tells use that at equilibrium the ratio must be 0.30. Technically we should back calculate from the equilibrium concentrations to the initial concentrations. However, for buers the equilibrium concentrations of the acid and the conjugate base do not dier signicantly from the starting concentrations. Thus one way to make this buer would be to mix, say, 50 mL of a 0.2 M solution of HC2 H3 O2 with 50 mL of a 0.06 M solution of NaC2 H3 O2 . pKa = log 1.7 105 = 4.77
Group Work
1. How would you make an acetate buer that has a pH of 5.00 (Ka = 1.7 105 )? 2. What would the pH of an acetate buer made by combining 50 mL of a 1.00 M HC2 H3 O2 solution with 50 mL of a 1.25 M NaC2 H3 O2 solution? 3. 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 buer for. Why? 4. Let say you wanted to hold your pH to within 0.1 pH unit around the pKa of acetic acid. What is the acceptable [C2 H3 O ] 2 range of the ratio [HC2 H3 O2 ] ?
68 MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION
Homework
Problems: Chapter 18: 11, 13, 15, 17, 18
MORE ON BUFFERS: THE HENDERSON-HASSELBALCH EQUATION 69
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. We learned that titrations are important techniques for determining the concentration of the analyte. We now revisit titrations armed with our knowledge of acid base equilibria.
Titration of a Strong Acid with a Strong Base

The simplest case of a titration reaction, and one we could handle last semester, is that involving a strong acid and a strong base. Since both the analyte and the titrant are strong electrolytes they fully dissociate and therefore fully react. Example: 25 mL of a 0.100 M HCl solution is titrated with 0.100 M NaOH. Calculate the titration curve for this process. This titration reaction is HCl + NaOH NaCl + H2 O The total number of moles of HCl is 0.025 L 0.100 mol HCl = 0.0025 mol HCl 1L (17.2) (17.1)
This problem breaks into three parts, i) before the equivalence point, ii) the equivalence point and iii) after the equivalence point.
TITRATIONS PART I 71
Before the equivalence point NaOH is the limiting reagent. If X L of NaOH is added then 0.100 M NaOH X L = 0.1X mol NaOH 1L (17.3)
have reacted with the HCl. Thus 0.0025 0.1X moles of HCl remains. Then, + 0.0025 0.1X H = 0.025 + X 0.0025 0.1X pH = log 0.025 + X (17.4)
At the equivalence point the HCl and NaOH exactly neutralize one another and the pH= 7.00. This occurs at 0.0025 mol HCl 1 mol NaOH 1 L NaOH = 0.025 L NaOH 1 mol HCl 0.100 mol NaOH (17.5) After the equivalence point HCl is the limiting reactant. If Y L of NaOH is added then Y L NaOH 0.100 mol NaOH = 0.1Y mol NaOH 1L (17.6)
have been added. Of these moles 0.0025 mol react with the HCl leaving 0.1Y 0.0025 mol NaOH unreacted. From this 0.1Y 0.0025 OH = 0.025 + Y 0.1Y 0.0025 pOH = log 0.025 + Y Thus, 0.1Y 0.0025 pH = 14 log 0.025 + Y (17.7)
(17.8)
The titration curve is shown in the gure below

72
TITRATIONS PART I
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 = 1.4 105 , 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. Lets say X mL of NaOH is delivered thus 0.1X mol of NaOH reacts fully with the niacin.
TITRATIONS PART I 73
This leaves 0.00250.1X 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 0.00250.1X 0.1X 0 0.025+X 0.025+X x x x 0.00250.1X 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 = 0.00250.1X 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 1010 . Ka So, (x) (x) . Kb = 7.1 1010 = 0.05 x
74 TITRATIONS PART I
Rearranging and using the quadratic formula gives x = [OH ] = 6.0 106 . The pH is then pH = 14 log 6.0 106 = 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 gure 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
18
TITRATIONS PART II
With lecture and the group work problems we have tackled titrations with monoprotic acids and bases. 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 0.10 M solution of vitamin C (H 2 C 6 H 6 O 6 ) is titrated with 0.10 M NaOH. The Ka1 = 7.9 105 and Ka2 = 1.6 1012 . Now the titration process will experience two equivalence points. Because Ka1 Ka2 we take separate the process into two parts: Reaction with the rst 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. Instead, we will simply calculate the pH at each equivalence point. The rst equivalence point is controlled by the Ka1 = 7.9105 reaction. So we take the NaOH to fully react with the rst proton of vitamin C. This occurs at 25 mL of NaOH added. Or, 0.025 L 0.10 mol HC6 H6 O 6 = 0.0025 mol HC6 H6 O . 6 1L
77
TITRATIONS PART II
Thus the concentration of HC6 H6 O is 6 0.0025 mol HC6 H6 O 6 = 0.05 M HC6 H6 O 6 0.050 L This HC6 H6 O then goes back towards the acid via the conju6 gate base reaction, HC6 H6 O + H2 O H2 C6 H6 O6 + OH 6 So we need the Kb1 which is Kw Kb1 = = 1.27 1010 Ka1 The ICE chart is HC6 H6 O OH [H2 C6 H6 O6 ] 6 I 0.05 0 0 C x x x 0.05 x x x E Using the Kb1 equation and solving for x = OH = 2.52 106 . Thus, pH = 14 log 2.52 106 = 8.40 Now, for the second equivalence point we repeat the procedure. The second equivalence point occurs at the addition of a total of 50 mL of NaOH. 0.0025 mol = 0.033 M. C6 H6 O = 6 0.075 L Now we need the Kb2 which is Kw = 6.25 103 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 0.033 0 0 x x x C E 0.033 x x x So,
Using the Kb2 equation and solving for x we get x = OH = 0.0116. Thus pH = 14 ( log [0.0116]) 12.06
78
TITRATIONS PART II
Group Work
1. Work out several values of the titration curve for the example above.
Homework
Reading: Kotz and Treichel, 18.3 Problems: Chapter 18: 23, 24, 25, 29, 79, 83
TITRATIONS PART II
79
80
TITRATIONS PART II
19
SOLUBILITY OF WEAK ELECTROLYTES
We have been applying our ideas about equilibrium to acid base reactions. 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, n n Ksp = Ana + c B nc a .
Remember the Anc Bna (s) is a solid so we do not include it in the equilibrium constant. For example of the solubility product for Fe2 (SO4 )3 is 2 3 Ksp = Fe3+ SO2 4
In the rst semester we simply learned ionic compounds as strong electrolytes, weak electrolytes and nonelectrolytes The solubility product gives us a way of ranking how soluble a compound is. For example Ca(OH)2 has a Ksp of 5.5105 whereas CaF2 has a Ksp = 5.3 1010 . We can say, quantitatively that Ca(OH)2 is more soluble then CaF2 . Lets say we want to know the concentration of Ca2+ and OH upon putting solid Ca(OH)2 into a beaker.
SOLUBILITY OF WEAK ELECTROLYTES 81
We write the solubility reaction Ca(OH)2 Ca2+ + 2OH and 2 Ksp = 5.5 105 = Ca2+ OH
From the stoichiometry of the reaction 2x moles of OH is produced for every x moles of Ca2+ thus 5.5 105 = (x) (2x)2 4x3 = 5.5 105 5.5 105 x3 = r 4 5 3 5.5 10 x = 4 x = 0.024 Thus Ca2+ = x = 0.024 M and OH = 2x = 0.048 M. pH = 14 ( log 0.048) pH = 12.6
We can take this further and determine the pH of the solution.
Group Work
1. Write the solubility product for (a) copper II sulde (b) zinc II hydroxide (c) lead II iodide 2. Put the solubility reaction we did in class into the ICE chart formalism. 3. The common ion eect occurs in solubility reactions as well as acid-base reactions. How would the common ion eect work here? Can you setup an ICE chart that will handle the common ion eect?
82 SOLUBILITY OF WEAK ELECTROLYTES
Homework
Reading: Kotz and Treichel, 18.4, 18.5, 18.6, 18.7 Problems: Chapter 18: 35, 37, 39, 45, 47, 53, 55, 59, 65, 67
83
84
20
REVIEW FOR EXAM 2
REVIEW FOR EXAM 2
85
Material for Exam III
86
REVIEW FOR EXAM 2
21
REVIEW OF THE FIRST LAW, ENTHALPY, AND HESS LAW
Last semester we tackled several ideas from thermodynamics. Now, over the next several lectures, we will complete the picture. But rst we need to review the key ideas from the rst semester.
The First Law of Thermodynamics

The rst law of thermodynamics is simply a statement of the conservation of energy for a system. In words the rst 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. The rst law is stated mathematically as 4E = q + w. (21.1)
Energy that enters or leaves a system is classied as either work or heat. As system here means any macroscopic piece of matter such as a beaker of water or an iron bar. Any work, w, done on the system is by convention taken to be a positive quantity Any work done by the system is then negative.
87
Likewise any heat, q, taken in by the system is by convention a positive quantity (endothermic) Any heat given o by the system is negative (exothermic).
Enthalpy
Let us consider applying the rst 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.
Since we are adding heat to the system, q > 0. Since the system is doing work, w < 0.
88
The rst law for this case says 4E = q(positive) + w(negative) Therefore no matter what 4E < q (21.3) (21.2)
So the change in total energy is less than the amount of heat energy we added to the system. 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 dened a new measure of energy called enthalpy (H) Enthalpy is dened such that at constant pressure it is equal to the amount of heat energy taken in by the system 4H qP , (21.4)
where the subscript P reminds us that this is true only for constant pressure. (We will always work at constant pressure in this course.) 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 o by a reaction. In fact, you will do this in lab. If the heat is measured at constant pressure then it is simply the change in enthalpy for the reaction: 4H = Hproducts Hreactants (21.5)
If 4H is positive that means that qP is positive and heat energy is taken in by the system. Reactions with positive 4H are called endothermic reactions. If 4H is negative that means that qP is negative and heat energy is given o by the system. Reactions with negative 4H are called exothermic reactions.
REVIEW OF THE FIRST LAW, ENTHALPY, AND HESS LAW 89
Hess Law
Both total energy, E, and enthalpy, H, are what are called state functions A state function is a function that depends only on the particular state that the system is in. It is completely independent of how the system arrived at that state. For example consider heating in water from 300 K to 310 K. You would calculate the same 4H or 4E regardless as to whether you heated directly from 300 K to 310 K or if you rst cooled to 290 K then heated to 360 K and then cooled to 310 K. 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, 4H for the overall reaction is the sum of the 4Hs for the component reactions. That is 4H is solely determined by 4H = Hproducts Hreactants regardless of how the reactants became the products. For example, 4H for the reaction 2C6 H6 + 15O2 12CO2 + 6H2 O (21.7) (21.6)
is the same as the sum of the 4Hs for the following reactions 2C6 H6 12C + 6H2 12C + 6H2 + 15O2 12CO2 + 6H2 O (21.8) (21.9)
Hesss law is very handy because it would be impossible to measure enthalpy changes for every imaginable reaction were it not for Hess law.
90 REVIEW OF THE FIRST LAW, ENTHALPY, AND HESS LAW
Group Work
1. Based on your experience, is 4H positive or negative for combustion reactions? 2. Use Hess law to determine 4Hrxn for 4NH3 + 5O2 4NO + 6H2 O given the following data N2 + O2 2NO; 4H = 180.6 kJ N2 + 3H2 2NH3 ; 4H = 91.8 kJ 2H2 +O2 2H2 O; 4H = 483.7 kJ 3. Based on the previous problem what is 4Hrxn for 5 2NH3 + O2 2NO + 3H2 O 2
Homework
Problems: Chapter 6: 27, 43, 45, 47, 49, 51, 53
91
92
22
ENTROPY
Up to this point our discussion of thermodynamics has focussed on energy (either total energy or else enthalpy). There is an equally important concept in thermodynamics called entropy. A simple way of thinking about entropy is that it provides a measure of disorder in a system. That is, for a given system, higher entropy means the system is disordered whereas low entropy means the system is ordered. 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 Congurations

One can get a feel for entropy by considering the possible arrangements of the molecules in a system. This requires a few denitions. Ensemble: The collections of molecules in a macroscopic system Microstate: One single arrangement of the ensemble Conguration: Collection of indistinguishable microstates. Given the symbol W
ENTROPY
93
Entropy: Proportional to the number of congurations through the Boltzmann equation S = k ln W, where k = 1.38 1023 J/K is the Boltzmann constant. WorkSheet on Microstate and Conguration (22.1)
Group Work
1. How many dierent ways are there to permute the letters in CAT? Call each permutation a microstate then collect equivalent microstates into congurations. How does the number of microstates compare to the number of congurations? 2. Repeat the about for ANN 3. Multiply the Boltzmann constant time Avogadross number. Do you recognize the number? 4. The so-called thermal energy per molecule is kT . Verify that it as proper units and calculate it for room temperature. 5. The so-called thermal energy per mole is RT . Verify that it as proper units and calculate it for room temperature.
Homework
Reading: Kotz and Treichel, 19.1, 19.2, 19.3 Problems: Chapter 19: 1,3
94
ENTROPY
23 THE SECOND AND THIRD LAWS
Entropy forms the basis for the second and third laws of thermodynamics. The mathematical statement of the second is for any spontaneous process T 4S q. (23.1) For isolated systems in which no heat energy can be exchanged with the environment T 4S 0 4S 0. This leads to the important result that 4Suniverse = 4Ssys + 4Senv 0 (23.3)
(23.2)
That is for every event the entropy of the universe increases. Now it is important to realize that 4Ssys need not be greater than zero. Natural processes can occur that lower the entropy of the system. If this happens, however, the change in entropy of the environment must be positive and outweigh that of the system. 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. The third law puts entropy on an absolute scale like temperature. This is in contrast to energy which can not be put on an absolute scale so only energy dierences have meaning.
THE SECOND AND THIRD LAWS 95
So we can not say a glass of water as and energy of so-and-so, but we can say it has an entropy of so-and-so.
Calculating Entropy
Like we learned for enthalpy, entropy is calculated in a similar manner. That is 4S is solely determined by 4S = Sproducts Sreactants regardless of how the reactants became the products. For example, 4S for the reaction 2C6 H6 + 15O2 12CO2 + 6H2 O (23.5) (23.4)
is the same as the sum of the 4Ss for the following reactions 2C6 H6 12C + 6H2 12C + 6H2 + 15O2 12CO2 + 6H2 O (23.6) (23.7)
We can also short cut the Hess law calculations by using the entropies of formation tables in Appendix L of the book. X
Sf,products
4S =
Sf,reactants
(23.8)
Group Work
1. Use either the entropy as a measure of disorder concept of the number of congurations 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
(b) condensing of water vapor (c) the reaction between hydrogen and oxygen to form water (d) dissolution of NaCl in water 2. 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 molK NH3 193 CO2 214 NH2 CONH2 174 H2 O 70 3. What is 4rxn S for NH3 + CO2 NH2 CONH2 + H2 O
Homework
THE SECOND AND THIRD LAWS
97
98
THE SECOND AND THIRD LAWS
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. 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. For example consider water at room temperature and pressure. If only enthalpy was a factor than the water would be in the solid state. Conversely, if only entropy was a factor, the water would be a vapor. Since both factors contribute to the nal state of water, it turns out that water is a liquid under these conditions.
The Second Law

If we consider the second law T 4S q. Now, for this course we are taking enthalpy to be heat energy (later in your career you will be more careful about this).
GIBBS FREE ENERGY 99
Hence, T 4S 4H. 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. We thus, dene what is called Gibbs free energy as the left hand side 4G = 4H T 4S. If 4G is negative the process will proceed, but if 4G is positive the process will reverse. Finally, if 4G is zero the process is at equilibrium.
Gibbs Free Energy

Notice how 4G captures natures great compromise between enthalpy and entropy. The denition 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. This energy is tied up and must be contained in the system. So if we consider 4H as the total energy available and T 4S as the tied up in randomizing the system, then 4H T 4S is energy free to do work. Hence the term free energy Succinctly we say the Gibbs free energy is the energy available to do work.
100 GIBBS FREE ENERGY
If 4G is negative then the free energy can be used to do work. 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. 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. Reactions can be energy driven, entropically driven, or both.
Group Work
1. Consider the following spontaneous processes and state whether they are energy drive, entropically driven, 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. (d) the rusting of iron 2. Consider the eect of temperature on 4G. (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
3. Like enthalpy and entropy, Gibbs free energy can be calculated using Hess law or free energies of formation. Calculate 4G for C2 H5 OH + 3O2 2CO2 + 3H2 O, given kJ substance 4G mol f C2 H5 OH 174.8 O2 0 CO2 394.4 H2 O 228.6
Homework
Reading: Kotz and Treichel, 19.6 Problems: Chapter 19: 19, 21, 23, 25, 27, 29, 31
102
GIBBS FREE ENERGY
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, it can tell us which way the reaction will proceed to get to equilibrium. Thus there must be some connection between 4rxn G and both the equilibrium constant K and the reaction quotient Q. Indeed there is a connection, unfortunately you will need to wait until later in your career to derive it from scratch. So, here we will simply state the relation. The equilibrium constant is related to 4rxn G by 4rxn G = RT ln K (25.1)
Remember 4rxn G is the dierence in free energies of the products and reactants under standard conditions (298 K, 1 atm, [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. The 4rxn G for the reaction under any conditions is given by referencing to 4rxn G and the reaction quotient, 4rxn G = 4rxn G + RT ln Q. (25.2)
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
The dierence between 4rxnG and 4rxnG

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

negative
z}|{
>1
(25.3)
Turning to 4rxn G, this tells us how the reaction will go under the current conditions of the reaction. So if we consider the case where we mix reactants to perform a reaction. Initially there are no products and therefore Q = 0 and we have z}|{ 4rxn G = 4rxn G + RT ln 0 =

(25.4)
So regardless of what 4rxn G , even if very reactant favored, initially there is a tremendous amount of thermodynamic force for the reaction to proceed. Then some products are formed but before we reach equilibrium Q < K. 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. 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. 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.

GIBBS FREE ENERGY AND EQUILIBRIUM 105
Group Work
1. LeChateliers principle is a consequence of the 4G equation. Use the 4G equation to mathematically show LeChatelierss principle. (Hint: the arguments will be similar to what we just discussed at the end of lecture. 2. Earlier, 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. Use the 4G equation to show these relationships.
Homework
106
26
REVIEW OF CONCEPTS SURROUNDING GIBBS FREE ENERGY
Worksheet
REVIEW OF CONCEPTS SURROUNDING GIBBS FREE ENERGY107
108REVIEW OF CONCEPTS SURROUNDING GIBBS FREE ENERGY
27
OXIDATIONREDUCTION 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. We rst need a few denitions. 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 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 species which has a tendency to be reduced is called an oxidizing agent. A general form for the oxidationreduction reaction is Ahigh + Dlow Alow + Dhigh . (27.1)
Here a species A accepts an electron from a donor species D. A is reduced since its oxidation number decreases and D is oxidized since its oxidation number increases For example an oxidationreduction reaction between copper sulfate and zinc metal is written as CuSO4(aq) + Zn(s) ZnSO4(aq) + Cu(s) . (27.2)
It is more illustrative to write the net ionic equation by cancelling the spectator sulfate ion Cu2+ + Zn0 Zn2+ + Cu0 . (s) (s) (aq) (aq)
OXIDATIONREDUCTION REACTIONS I
(27.3)
109
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+. 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. Zinc is oxidized and copper is reduced. Zinc acts as a reducing agent and copper acts as an oxidizing agent
Balancing redox reactions

It is important for you to become procient at balancing redox reactions. This requires practice. There are three cases one needs to consider. The rst is simply balancing redox reactions like the zinccopper example above. The second is balancing redox reactions in acids and the third is balancing redox reactions in bases See Koltz & Treichel Section 20.1, Examples 1,2 and 3
Group Work
1. Work on handout.
Homework
Reading: Kotz and Treichel, 20.1 Problems: Chapter 20: 1, 2, 3, 4, 5, 6 *Note* these are due after the next lecture.
110 OXIDATIONREDUCTION REACTIONS I
28
OXIDATIONREDUCTION REACTIONS II
We will continue practicing balancing Redox reactions
Group Work
1. Work on handout.
Homework
Reading: Kotz and Treichel, 20.1 Problems: Chapter 20: 1, 2, 3, 4, 5, 6
111
112
29
ELECTROCHEMICAL CELLS
We now consider the example of the Daniell cell. The reaction Zn(s) + Cu2+ (aq) Cu(s) + Zn2+ will occur spontaneously when mixed in a beaker. During the reaction electrons are transferred and the system moves to a lower energy state. However, all of the chemical energy evolved is lost as heat and no work can be extracted. (29.1)
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 (29.3) (29.2)
113
Cell diagrams
Conventions for writing down an electrochemical cell. 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. (29.4)
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 = right left
114
(29.5)
For the Daniell cell we get: z }| { 2 + |Zn Zn 2 + |Cu Cu cell

red. pot.!!
left (oxidation) right (reduction) cell reaction
Zn(s) + Cu2+ (aq) Cu(s) + Zn2+
Zn Zn2+ + 2e Cu2+ + 2e Cu
0.763 V 0.337 V 1.100 V
Group Work
1. To get a redox to go in reverse one must apply an opposing voltage in excess of the cell potential. This is how a battery recharger works. What voltage would need to be applied to a Daniel cell to recharge it. 2. What is the standard cell potential for 3Mg(s) + 2Al3+ (aq) 2Al(s) + 3Mg2+ (29.6)
3. How many electrons are transferred in the above reaction (be sure to consider the stoichiometry)?
Homework
Reading: Kotz and Treichel, 20.2, 20.3, 20.4, 20.5 Problems: Chapter 20: 7, 11, 13, 15, 17, 19, 21, 23
115
116
30
THE NERNST EQUATION
The cell potential allows one to determine the maximal work, wmax the cell can produce. That is, the amount of work to move n moles of electrons though a potential cell . wmax = nFcell where F = 96485 C/mol is Faradays constant. Once we know the maximal work for the cell, we can determine the free energy of the cell by
0 4rxn G = wmax = nFcell
(30.1)
(30.2)
As also have the 4G equation, 4rxn G = 4rxn G + RT ln Q, (30.3)

[products] where Q = [reactants] is the reaction quotient (remember we are not at equilibrium)
We can substitute 4rxn G = nFcell and 4rxn G = nF cell into the above equation to give the Nernst equation = RT ln Q nF (30.4)
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 = nF from above. It is of interest to study the Nernst equation at equilibrium. At equilibrium Q = K and = 0 since the cell can do no work. The Nernst equation then becomes z }| { RT ln K nF = RT ln K 0 = nF 4rxn G = RT ln K.
THE NERNST EQUATION
4rx n G
(30.5)
117
As we expected from earlier. Example: What is for a Daniel cell at 300 K when the concentration of Cu2+ is 0.100 M and the concentration of Zn2+ is 0.001 M? Zn(s) + Cu2+ (aq) Cu(s) + Zn2+ (30.6)
First we need which we found last lecture to be 1.10 V. Then we use the Nernst equation, = 1.10 = 1.04 V 8.314 300 0.100 ln 2 96485 0.001
The n = 2 because 2 electrons are transferred from the zinc to the copper during the reaction. Notice that even though the concentrations dier by a factor of 100, the dierence in voltage from the standard potential is minimal.
Group Work
1. Explicitly derive the Nernst equation from the 4G equation. 2. What is K for the Daniels cell reaction? Is it product favored or reactant favored? 3. We can also use a dierences in concentrations between to half cells to do work. These systems are called concentration cells. Consider Na(Hg)|NaCl(aq,M1 )||NaCl(aq,M2 )|Na(Hg) (30.7)
The double vertical lines ( || ) represent the salt bridge. left (oxidation) Na(Hg) Na+ (aq,M1 ) + e + |Na Na right (reduction) Na+ (aq,M2 ) + e Na(Hg) + |Na Na cell reaction
118
Na+ (aq,M2 ) Na+ (aq,M1 )
cell
2.714 V 2.714 V 0V
THE NERNST EQUATION
The Nernst equation becomes =0 RT [Na]1 RT [Na]1 ln ln = n F [Na]2 F [Na]2

1
(30.8)
So we see that if [Na]1 6= [Na]2 then a potential will develop. (a) What is the potential of a sodium concentration cell if the dierence 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, 20.6, 20.7, 20.8 Problems: Chapter 20: 25, 26, 27, 28, 29, 31, 33, 35, 37, 39, 45, 49
THE NERNST EQUATION
119
120
THE NERNST EQUATION
31
REVIEW FOR EXAM 3
REVIEW FOR EXAM 3
121
Additional Material for Exam IV
122
REVIEW FOR EXAM 3
32
REVIEW OF MOLECULAR GEOMETRY
We will be talking about the nature of intermolecular forces. These forces are determined and inuenced by the three dimensional geometry of the molecule. Thus we need to review the molecular geometry material from the rst semester.
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. For covalent compounds the electron density is shared. However, it is not necessarily shared evenly between all the atoms in the compound. As a result some atoms in the compound carry what are called partial charges. One way to characterize the charge distribution in compounds and polyatomic ions is to introduce the idea of electronegativity, . Electronegativity is a measure of the ability of an atom in a compound to attract electron density to itself.
See Figs. 9.8, 9.9 and 9.11 of Kotz&Treichel

REVIEW OF MOLECULAR GEOMETRY 123
For any given bonded pair the dierence in electronegativities will determine just how equally the atoms share the bonding electrons. As a rule of thumb, if the electronegativities for the bonding pair dier by less than 0.5 then they essentially equally share the electrons. This type of bond is called a nonpolar covalent bond. if the electronegativity dierence is between 0.5 and 2.0 then one atom attracts more electron density. This type of bond is called a polar covalent bond. The atom with the higher electronegativity carries a partial negative charge while its partner with lower electron density carries a positive charge. if the electronegativity exceeds 2.0 the bond is an ionic bond.
VSEPR Model
Prior to discussing valence bond theory we need to learn something about the shapes of molecules. A good approach to this is given by the valence shell electron repulsion (VSEPR) model. 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. Under the VSEPR model molecules can be classied according to there electronic geometry. The electronic geometry is the three dimensional structure that the electron densityeither a bond or lone pairadopts. 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
Trigonal-bipyramidal: Five bonds or lone pairs Octahedral: Six bonds or lone pairs Once the molecule has been assigned its electronic geometry, it then gets assigned its molecular geometry. Molecular Geometries (electronic geometry in bold, molecular in italic) Linear Linear: Two bonds, no lone pairs. Trigonal planar Trigonal planar: Three bonds, no lone pairs. Bent: Two bonds, one lone pair. Tetrahedral Tetrahedral: Four bonds, no lone pairs. Trigonal Pyramidal: Three bonds, one lone pair. Bent: Two bonds, two lone pairs. Trigonal-bipyramidal Trigonal-bipyramidal: Five bonds, no lone pairs. Seesaw: Four bonds, one lone pair. T-shaped: Three bonds, two lone pairs. Linear: Two bonds, Three lone pairs. Octahedral Octahedral: Six bonds, no lone pairs. Square-pryamidal: Five bonds, one lone pair. Square-planar: Four bonds, two lone pairs.
REVIEW OF MOLECULAR GEOMETRY 125
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 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. If all the polar bonds in a molecule cancel each other out then the molecule has no net dipole moment.
Group Work
1. Give the electronic and molecular geometries of the following molecules. Also indicate the direction of the dipole moment (a) NH3 (b) H2 CCl2 (c) BF3
126 REVIEW OF MOLECULAR GEOMETRY
Homework
Problems: Chapter 10: 1, 3, 5, 7, 9, 11
127
128
33
INTERMOLECULAR FORCES
Polarizability and Induced Dipoles
Last time we reminded ourselves of the molecular dipole moment. The dipole moment is important in determined intermolecular forces and the physical properties of substances. Another equally important and somewhat related property of the molecule is its polarization. The polarization, , is a measure of how the electron density of the molecules responds to an external electric eld. An external electric eld causes the electron cloud of a molecule to become distorted. This distortion means that, even for neutral molecules, there can exits a dipole moment. Unlike the permanent dipole moment that comes from appropriate molecular geometry, this induced dipole is caused by the presence of the electric eld, , = (33.1)
129
Figure 1
Figure 2
Intermolecular Forces
There are several types of intermolecular forces that dier in there make-up and in there interaction length.
The Coulombic Forces IonIon: The force between two ions is the strongest molecular force and it has the longest interaction length. The force, F , falls o relatively slowly with distance, r, F 1 r2 (33.2)
Iondipole: This force is weaker than ionion interaction and it falls o with distance quicker, 1 (33.3) F 3 r
130 INTERMOLECULAR FORCES
Figure 3
Figure 4 The Van der Waals Forces Even when ions are not present one still sees intermolecular forces. These forces are called Van der Waals forces. The Van der Waals forces are weaker than the coulombic forces. They also have a shorter interaction length dipoledipole: The strongest of the Van der Waals forces with the longest interaction length, 1 (33.4) F 4 r dipoleinduced dipole: When a molecule has a permanent dipole, that dipole creates an electric eld that neighboring molecule feel. Consequently, an induced dipole can be created in the neighboring dipole. As you might expect these forces are weaker
INTERMOLECULAR FORCES 131
Figure 5
Figure 6 then dipoledipole forces, having the form of F 1 r5
induced dipoleinduced 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 uctuating. This random uctuation spontaneously creates a transient dipole moment which can then induce a dipole in a neighboring molecule. This induced dipole then strengthens the transient dipole by back induction.
132 INTERMOLECULAR FORCES
The force is very weak and drops o very rapidly, F 1 r6
Group Work
1. 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
133
134
34
HYDROGEN BONDING AND WATER
Last time we discussed intermolecular forces. There is one very important and special type of intermolecular force that we did not mention: hydrogen bonding. Hydrogen bonding can occur in between some molecules that contain hydrogen. If a hydrogen is bonded to an oxygen, nitrogen or uorine atom in one molecule, it can hydrogen bond to an oxygen, nitrogen or uorine atom in another molecule. A hydrogen bond can be thought of as either an exceptionally strong physical interaction or a very weak chemical bond. Molecules that have a hydrogen bonded to an oxygen, nitrogen or uorine atom can be hydrogen bond donors and acceptors. Molecules that have an oxygen, nitrogen or uorine atom but no hydrogen attached to it can only be hydrogen bond acceptors.
Figure 1
HYDROGEN BONDING AND WATER 135
Figure 2
Figure 3
136
Water
One of the most interesting, important and complicated substances know is water. We dont always appreciate how unique water is because we are so familiar with it. Almost all of the unique aspects of water are do to hydrogen bonds. Some of the unique properties of water are An abnormally high melting point An abnormally high boiling point The fact that ice oats The Grotthuss mechanism A high heat capacity A high dielectric constant.
Group Work
1. Restate in your own words why hydrogen bonding is the reason for the unusual properties of water that we discussed in lecture.
Homework
Reading: Kotz and Treichel, 13.3, 13.4, 13.5 Problems: Chapter 13: 7, 8, 9, 10, 11, 13, 15, 17, 19, 21
137
138
35
PHASE DIAGRAMS
The phase change behavior of a substance can be expressed conveniently with a pressure versus temperature graph called a phase diagram. HANDOUT The lines on the phase diagrams represent the precise temperatures and pressures where an equilibrium between two phases occurs. The solidliquid line: crossing the line from solid to liquid represents melting crossing the line from liquid to solid represents freezing The gasliquid line: crossing the line from gas to liquid represents condensation crossing the line from liquid to gas represents boiling The solidgas 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. The triple point The point where the solid-liquid line, solid-gas line and gas-liquid line converge.
PHASE DIAGRAMS 139
The single value of temperature and pressure in which all three phases can co-exist. The critical point The termination of the gas-liquid line.
Group Work
1. How would the slope of the solid liquid line for the phase diagram for water compare to the generic one shown in the handout. 2. Suggest a way to go from a liquid to a gas without boiling. 3. Is there a way to go from a solid to a liquid without melting?
Homework
Reading: Kotz and Treichel, 13.6 (skim), 13.7 (skim), 13.8 (skim), 13.9, 13. 10 Problems: Chapter 13: 31, 33, 34, 35, 36, 37
140
PHASE DIAGRAMS
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. The phrase like dissolves like captures the determining factors in the dissolution process. 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 specic 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 energy of interaction between solvent molecules the net entropy gain or loss due to dissolution.
Liquid-liquid solutions
The specic 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 specic 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 proteinwater solution to cause the protein to precipitate out as a solid. Why might this happen?
Homework
143
144
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.
Henrys 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.
145
This relation is called Henrys law and is Xi = ki Pi (37.1)
where Xi is the mole fraction of the solute, Pi is the partial pressure and ki is the Henrys law constant. Henrys law is related to LeChateliers principle. If we consider the equilibrium establishing in the closed container, we have solutesolution solutevapor If we where to increase the partial pressure of the solute in the vapor phase we would expect, by LeChateliers principle, that the reaction above would go in the reverse direction. We expect the mole fraction to go up. If we look at Henrys law, increasing the partial pressure makes the mole increase.
Raoults Law
Another relationship between the vapor phase partial pressures and the solution exist for the solvent.
According to Raoults law the partial pressure of the solvent in the vapor phase above the solution is Ps = Xs Ps ,
146 PROPERTIES OF SOLUTIONS
where Ps is the vapor pressure, i.e, the partial pressure above pure solvent. Deviations from Raoults Law Raoults law is a purely statistical law. It does not require any kind of interaction among the constituent particle making up the solution. Since, in reality, there are specic interactions between particles, real solutions generally deviate from Raoults law. The physical interpretation of deviation from Raoults law is positive deviation: the molecules prefer to be around themselves rather than other types of molecules. negative deviation: the molecules prefer to be around other types of molecules than themselves. no deviation: the molecules have no preference.
Positive deviation from Raoults lawNegative deviation from Raoults law
Colligative properties
Interestingly, certain physical properties always change the same way as a small amount of solute is added to a solvent. The properties that do this are called colligative properties. We will only discuss boiling point and freezing point.
147
When a small amount of solute is added to a solvent the boiling point is always initially elevated. This phenomenon is called boiling point elevation. Eventually as more solute is added the boiling point might decrease depending on the nature of the solute. The initial boiling elevation, however, is independent of the nature of the solute. As similar phenomenon occurs for freezing points. But, in this case, the freezing point is lowered when a small amount of solute is added. This is called freezing point depression. Again, as more solute is added the freezing point might begin to increase.
Group Work
1. What are the units on Henrys law constant? 2. Sometimes Henrys law is expressed in terms of concentration, [i] = ki Pi , now what would the units of Henrys law constant be? 3. For liquidliquid mixtures it is not always clear what the solute is and what the solvent is. As one liquid moves from a high mole fraction to a low mole fraction, we would expect the liquid to rst obey Raoults law than to obey Henrys law. What must be true for about the relation between the vapor pressure and the Henrys law constant for the liquid to obey both laws at all mole fractions?
148 PROPERTIES OF SOLUTIONS
Homework
Reading: Kotz and Treichel, 14.3, 14.4 Problems: Chapter 14: 21, 23, 25, 27, 29, 33, 37, 39, 41, 47, 51, 55
149
150
38
REVIEW FOR FINAL EXAM
REVIEW FOR FINAL EXAM
151

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General Chemistry II Chemistry 128

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

. . . . . . . . . . Acids and Bases . . . . . . . . . . . . . . . . . . . .

99 99 100 101 102

Material for Exam I

DIFFERENTIAL RATE LAWS

The Reaction Rate

DIFFERENTIAL RATE LAWS

Elementary Reactions and Molecularity

DIFFERENTIAL RATE LAWS

3 DETERMINATION OF RATE LAWS

Dierential methods based on the rate law

2. Method of isolation for v = k[A]x [B]y rate laws

ood with, say, A so v kax [B]y

[A]95% 20 min 10 min 10 min

Likewise from runs II and III vII = and (3.3)

DETERMINATION OF RATE LAWS

DETERMINATION OF RATE LAWS

INTEGRATED RATE LAWS

= k[I] = k[I]2 = k[I]n k[I] = km +[I]

Linearizing the integrated rate laws

INTEGRATED RATE LAWS

INTEGRATED RATE LAWS

INTEGRATED RATE LAWS

INTEGRATED RATE LAWS

THE ARRHENIOUS EQUATION

Temperature Dependence of the Rate Constant

1 If ln k is plotted versus T we get a straight line whose slope is Ea and intercept is ln A. R

Application of the Arrhenious Equation

Ea Ea = ln 1.5 . 400R 300R

1 1 k298 Ae 298R 50500( 273R 298R ) = 50500 = e k273 Ae 273R = 6.47.

So the reaction goes 6.47 times faster at 298 K than at 273 K.

THE ARRHENIOUS EQUATION

KINETICS AND EQUILIBRIUM

but also the reverse reaction,

These can be written as one reaction with a double arrow, aA + aB cC + dD.

KINETICS AND EQUILIBRIUM

EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT

The Equilibrium Constant

EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT

EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT

We can rearrange this to give 492x3 984x2 + 616x 123 = 0 (8.3)

Unfortunately we are now faced with a cubic equation to solve.

For this example, p 0.4232 4 (0.141) x = 2 x = 0.642, x = 0.219. 0.423

9 THE REACTION QUOTIENT AND LECHATELIERS PRINCIPLE

The Reaction Quotient

38 THE REACTION QUOTIENT AND LECHATELIERS PRINCIPLE

40 THE REACTION QUOTIENT AND LECHATELIERS PRINCIPLE

REVIEW FOR EXAM 1

REVIEW FOR EXAM 1

Material for Exam II

REVIEW FOR EXAM 1

ACIDS AND BASES

Brnstad Acids and Bases

Conjugate Acid-Base Pairs

CH3 CO2 H + NH3 CH3 CO + NH+ 2 4 H2 S + H2 O HS + H3 O+

ACIDS AND BASES

ACIDS AND BASES

We can write the equilibrium constant for this reaction as K = Kw = H3 O+ OH . (12.2)

The pH of Strong Acids and Bases

From the 14 =pH + pOH relationship

ACID AND BASE EQUILIBRIA

ACID AND BASE EQUILIBRIA

14 REACTIONS WITH WEAK ACIDS AND WEAK BASES