Chemistry 18

CHEMISTRY 18
The Fundamentals of General Chemistry II

Geoffrey C. Li
Department of Physical Sciences and Mathematics
Summer || AY 2010-2011 || Section A

Monday to Friday: 7:30-9:30 AM RH 119 Notes by Alvin J. Logronio
Table of Contents
Calculus Review
Linear Regression (Least Squares Method)
Chemical Kinetics
Rate3
Theories on Reaction Rate 4
Factors Affecting Reaction Rate 4
Methods for Determining the Rate Law 5
Dependence of the Concentration of Reactants with Time (Integrated Rate Laws)7
Gas-Phase Reactions 10
Reaction Mechanisms 13
Nuclear Chemistry
Type of Nuclear Reactions 17
Effect of Radiation on Biological Matter 20
Chemical Thermodynamics
First Law of Thermodynamics (Law of Conservation of Energy) 22
Thermochemistry25
Second Law of Thermodynamics 29
Third Law of Thermodynamics 33
Chemical Equilibrium
Approaches to Equilibrium 33
Molecular Equilibrium 35
Factors Affecting Equilibrium 38
Ionic Equilibria
Theories on Acids and Bases 40
Ionization of Water 41
Strong Electrolytes 41
Weak Electrolytes 42
Polyprotic Acids 42
Salts42
Common Ion Effect 43
Buffer Solutions 44
Acid-Base Indicators 44
Acid-Base Titration 45
Complex Ion Equilibrium 45
Slightly Soluble Salts 45
Factors Affecting Solubility 45
Precipitation46
Dissolution46
Electrochemistry
Electrochemical Cell 47
Thermodynamics of Electrochemical Cells 48
Electrolytic Cells 51
Faraday's Law of Electrolysis 52
Coordination Chemistry
Complex / Coordination Compound 53
Ligands54
Nomenclature of Complexes 55
Isomerism56
Structural Isomers 56
Optical Isomers (Enantiomers) 56
Theories on Bonding 57
Valence Bonding Theory (Localized Electron Model) 57
Crystal Field Theory 58
Reactions60
Applications of Coordination Chemistry 61
ii | Chemistry 18: Fundamentals of General Chemistry II

Calculus Review
Differentiation: finding the slope of the tangent line
- represented by f'(x), dy/dx or y'
Properties
1. y = C y = 0
2. f (x) = xn f (x) = nxn1

Example: f (x) = 4x3 f (x) = 3(4)x31 = 12x2
3. d(u + v) = du + dv
Example: f (x) = 3x2 2x + 4 f (x) = 6x 2
4 10
Example: y = 5x 3 + 2 y = 5 + 4x2 20x3
x x
= 5x 3 4x1 + 10x2
4. d(uv) = udv + vdu or 1d2, 2d1

Example: f (x) = (3x 5)(4x2 3) f (x) = (3x 5)(8x) + (4x2 3)(3)
u vdu udv ldh hdl

5. d or
v v2 l2
2
4x + 3x 5 (2x + 1)(8x + 3) (4x2 + 3x 5)(2)
Example: f (x) = f (x) =
2x + 1 (2x + 1)2
6. Chain Rule
Example: f (x) = (4x2 7x + 13)2 f (x) = 2(4x2 7x + 13)(8x 7)
Integration: finding the area under the curve

xn+1
n +C if n = -1
Indefinite Integration x dx = n+1
ln|x| + C if n = -1
Examples:

x2
1. xdx = +C
2

2. 3 dx = 3 dx = 3 x0 dx = 3x + C

5 3
3. 5x2 dx = 5 x2 dx = x +C
3

x x
4. 3x2 + 14 dx = 3x2 dx dx + 14 dx
4 4
x3 x2
=3 + 14x + C
3 8
1
= x3 x2 + 14x + C
8

10 12
5. 5 + 2 dv = 5 dx 10v 1 dx + 12v 2 dx
v v
12 1
= 5v 10ln|v| + v +C
1
= 5v 10ln|v| 12v 1 + C
Geoffrey C. Li Notes by A-Log | 1

b
Definite Integration f (x) dx
a
Examples:
4
1. (x + 2) dx
2
4 4
= x dx + 2 dx
2 2
4
x 2
= + 2x
2 2
2 2
4 2
= + 2(4) + 2(2)
2 2
= 16 6 = 10
1
3 1 2
2. 4x + 2x 3x + dx
2
1
1 1 1 1
3 2 1
= 4x dx + 2x dx 3x dx + dx
2
1 1 1 1
1
x x 4
x 1 3 2
= 4 + 2 3 + x
4 3 2 2 1
1
2 3 1
= x4 + x3 x2 + x
3 2 2 1

2 3 1 2 3 1
= (1)4 + (1)3 (1)2 + (1) (1)4 + (1)3 (1)2 + (1)
3 2 2 3 2 2
7
=
3
2t

3. 7t 3 4t1 + 10t2 dt
t
2t
t2 t1
= 7 3t 4ln|t| + 10
2 1 t
2t
7
= t2 3t 4ln|t| 10t1
2 t
7
= (2t) t 3 (2t t) 4 (ln|2t| ln|t|) 10 (2t)1 t1
2 2
2
7 2 2t t
= 3t 3t 4 ln 10
2 t 2t2
21 2
= t 3t 4ln2 5t1
2
2 | Chemistry 18: Fundamentals of General Chemistry II

Linear Regression (Least Squares Method)
- to know if there is a linear relation between two variables
- gets the best-fit line between a set of points
r = correlation coefficient in a calculator: y = A + Bx

ranges from -1 to 1, -1/1 means a straight line A = y int B = slope
y = the value of y when x is... x = the value of x when y is...

Example: 20y Example: 20x
Example: x y r = 0.999228
15 18
12.5 15 A = 0.3086
12 14.3 B = 1.176
8 10 Equation: y = 1.176x + 0.3086
13.8 16.5
6.7 8
14.6 17.5
Chemical Kinetics
- branch of chemistry that deals with rates or speeds of reaction
- determines the factors that affect rates and its mechanisms
Rate
- in chemistry rate is
rate of appearance of the product = rate of disappearance of the reactant
For the reaction A + 2B C

d[C] d[A] 1 d[B]
Rate of reaction = = =
dt dt 2 dt
d[C] d[A] d[B]

if (rate C) = 0.1 M/s, then (rate A) = 0.1 M/s, (rate B) = 0.2 M/s
dt dt dt
1
Rate of reaction = 0.1 M/s = (0.1) M/s = (0.2) M/s
2
[B] is changing at the greatest rate
For the reaction: 3X + 5Y 2Z

1 d[Z] 1 d[X] 1 d[Y ]
Rate of reaction = = =
2 dt 3 dt 5 dt
[Y] is changing at the greatest rate
1
For the reaction: N2 O5 2N O2 + O2
2
1 d[N O2 ] d[O2 ] d[N2 O5 ]
Rate of reaction = =2 =
2 dt dt dt
[N O2 ] is changing at the greatest rate

Quiz:
d[N O]
Given: 4N H3(g) + 5O2(g) 4N O(g) + 6H2 O(g) = 0.60M/s
dt
1 d[N O] 1 d[H2 O] 1 d[N H3 ] 1 d[O2 ]
Rate = = = =
4 dt 6 dt 4 dt 5 dt
d[H2 O] 6 d[N O] 6
1: = = (0.60M/s) = 0.090M/s
dt 4 dt 4
d[O2 ] 5 d[N O] 5
2: = = (0.60M/s) = 0.075M/s
dt 4 dt 4
d[N H3 ] 4 d[N O] 4
3: = = (0.60M/s) = 0.060M/s
dt 4 dt 4
1 d[N O] 1
4: Rate of reaction = = (0.60M/s) = 0.015M/s
4 dt 4
Theories on Reaction Rate

1. Collision Theory
- for a reaction to occur, the reactant molecules must collide
- not all collisions are effective
Requirements for an effective collision

a. reactants must have the proper orientation
Example: CO + N O2 CO2 + N O
Ineffective: CO ON=O
Effective: OC ON=O
b. reactants must have sufficient energy to break bonds
- activation energy: minimum energy that is required for the reaction to
occur, energy barrier that must be overcome
- enthalpy (H) has nothing to do with the rate of the reaction
Ea, rate
rate of reaction frequency of collision

Ea
RT
k
= p + Z
+ e

rate constant steric factor (orientation) frequency of collision fraction of molecules with sufficient energy
2. Transition State Theory (Henry Eyring)

- all reactants pass through a transition state
- species in transformation
- shown in the peak of an energy profile
- highly energetic and highly unstable
- therefore, you cannot isolate the transition state
- collision is not necessary for the reaction to occur
- reaction can occur through bond weakening
- contains partial forming and partial breaking of bonds
Example: CO + O-N=O [OC--O--N=O] O=C=O + N=O
rate of reaction ease of formation of the transition state
- ease is related with the activation energy

Ea, ease of formation
Factors Affecting Reaction Rate

1. Nature of Reactants
- some reactions are naturally fast while others are naturally slow
Example: between Mg and Fe in water, Mg reacts faster
- the activation energy is dependent on the nature of the reactants
2. Surface Area SA, Rate

- when there is a larger surface area exposed to collision, the rate of reaction increases
3. Concentration of Reactants Concentration, Rate; Rate [reactants]n

- more molecules are available for collision
Rate Law: k = rate constant

n
rate = k[reactants] n = order of reaction
- the order of reaction is experimentally determined

- it is not equal to the coefficient in the balanced equation
Methods for Determining the Rate Law

a. Method of Initial Rates
- initial rate: rate at the first instant the reactants react
Example:
Given: A+2B C
[A] [B] Initial Rate (M/s)

0.010 M 0.010 M 1.2 104
0.010 M 0.020 M 2.4 104
0.020 M 0.010 M 4.9 104
a. Rate Law
rate = k[A]x [B]y
rate 3 k(0.020)x (0.010)y rate 2 k(0.010)x (0.020)y

A: = B: =
rate 1 k(0.010)x (0.010)y rate 1 k(0.010)x (0.010)y
x 4
y
4.9 104 0.020 2.4 10 0.020
= =
1.2 104 0.010 1.2 104 0.010
4.08 = 2x 2 = 2y
x=2 y=1
2
rate = k[A] [B]
Overall Order: 2+1=3

rate
Substitute Experiment 1: k =
[A]2 [B]
1.2 104
=
(0.010M )2 (0.01M ) Rate = (120 M 2 s1 )[A]2 [B]
= 120 M 2 s1
Double A? 4 Rate Double B? 2 Rate

2
[2A] [2B]? 8 Rate [2A]2 [0.5B]? 2 Rate
[0.5A]2 [2B]? 0.5 Rate
b. Differential Method
Rate = k[A]n Plot log Rate vs log [A]

log Rate = log k + n log[A] slope = n

y b mx y-int = logk

c. Isolation Method
rate = k[A]x [B]y [C]z
A: at constant [B] and [C]

log rate = log k[B]y [C]z + x log[A]

y b mx
Plot log rate vs log [A]

slope = x
y-int = log k[B]y [C]z
B: at constant [A] and [C]

log rate = log k[A]x [C]z + y log[B]

y b mx
Plot log rate vs log [B]

slope = y
y-int = log k[A]x [C]z
C: at constant [A] and [B]

log rate = log k[A]x [B]y + z log[C]

y b mx
Plot log rate vs log [C]

slope = z
y-int = log k[A]x [B]y
Example:
[A] [B] Initial Rate (M/s)
0.020 M 0.020 M 8.40 105
0.020 M 0.025 M 1.31 104
0.020 M 0.030 M 1.89 104
0.020 M 0.035 M 2.57 104
0.025 M 0.030 M 2.36 104
0.030 M 0.030 M 2.83 104
0.035 M 0.030 M 3.30 104
rate = k[A]x [B]y
A: at constant [B] B: at constant [A]

log rate = log k[B]y + x log[A] log rate = log k[A]x + y log[B]
Plot log rate vs log [A] Plot log rate vs log [B]
r = 0.99999 r = 0.999998
B = 0.996 1 = x B = 1.99 2 = y
A = 2.032 = log k[B]y A = 0.679 = log k[A]x
rate = k[A][B]2
log k[B]y = 2.0315 log k[A]x = 0.67912

log k(0.030)2 = 2.0315 log k(0.020) = 0.67912
k(0.030)2 = 102.0315 k(0.020) = 100.67912
k = 10.33 M 2 s1 k = 10.47 M 2 s1
Quiz:
[HgCl2 ] [C2 O2
4 ] Initial Rate (M/s)
0.164 M 0.15 M 3.20 105
0.164 M 0.45 M 2.90 104
0.164 M 0.90 M 1.15 103
0.164 M 1.80 M 4.61 103
0.082 M 0.45 M 1.40 104
0.041 M 0.45 M 7.25 105
0.021 M 0.45 M 3.71 105
rate = k[HgCl2 ]x [C2 O42 ]y
[C2 O2
4 ]: at constant [HgCl2 ] [HgCl2 ]: at constant [C2 O2
4 ]
log rate = log k[HgCl2 ] +x
y log[C2 O42 ] log rate = log k[C2 O42 ]y + x log[HgCl2 ]
Plot log rate vs log [C2 O2

4 ] Plot log rate vs log [HgCl2 ]
r = 0.9999 r = 0.9999
slope = y = 1.99 2 slope = y = 0.995 1
rate = k[HgCl2 ][C2 O42 ]2
From constant [C2 O2

4 ]: When [HgCl2 ] = 0.12 M and [C2 O2
4 ] = 0.10 M:
y-int = 2.76213 rate = (8.54 103 M 2 s1 )(0.12 M )(0.10 M )2
2.76213 = log k[C2 O42 ]2 rate = 1.02 105 M/s
2.76213 = log k(0.45)2
3 2 1
k = 8.54 10 M s
Dependence of the Concentration of Reactants with Time (Integrated Rate Laws)
- One-Reactant Type of Reactions
[A]0 = concentration at time 0 [A]t = concentration at time t
d[A]
rate = k[A]n rate =
dt
d[A]
= k[A]n
dt
d[A] d[A]
n=0: = k[A]0 n=1: = k[A]1
dt dt
[A]t
t [A]1 d[A] = k dt
d[A] = k dt [A]t
t
1
[A]0 0 [A] d[A] = k dt
[A]t [A]0 = k(t 0) [A]0 0
[A]t = kt + [A]0 [A]t

ln = k(t 0)
y mx b [A]0
ln[A]t ln[A]0 = kt
Plot [A] vs t ln[A]t = kt + ln[A]0
slope = -k
y mx b
y-int = [A]0
Plot ln[A] vs t
slope = -k
y-int = ln[A]0

d[A] d[A]
n=2: = k[A]2 n=3: = k[A]3
dt dt
[A]2 d[A] = k dt [A]3 d[A] = k dt
[A]t
t [A]t
t
2 3
[A] d[A] = k dt [A] d[A] = k dt
[A]0 0 [A]0 0
1 1 1 1
+ = kt + = kt
[A]t [A]0 2[A]2t 2[A]20
1 1 1 1
=
kt + 2 =
kt +
[A]t [A]0 2[A] 2[A]2
mx t mx 0
y b y b

1
1 Plot vs t
Plot vs t 2[A]2
[A]
slope = k
slope = k
1
1 y-int =
y-int =
2[A]20
[A]0
Summary of Integrated Rate Laws:

n=0: [A]t = kt + [A]0
n=1: ln[A]t = kt + ln[A]0
1 1
n=2: = kt +
[A]t [A]0
1 1
n=3: 2 = kt +
2[A]t 2[A]20
Example:
Given: 2C5 H6 C10 H12 [A]0 = 0.0400 M
t (sec) 0 50 100 150 200

[C5 H6 ] (M) 0.0400 0.0300 0.0240 0.0200 0.0174
1: Order of Reaction
n=0: Plot [A] vs t rn=0 = -0.967
n=1: Plot ln [A] vs t rn=1 = -0.9905
1 The reaction is a second-order reaction.
n=2: Plot vs t rn=2 = 0.999776
[A] rn=3 = 0.995
1
n=3: Plot vs t
[A]2
2: k slope = k = 0.163 M 1 s1
1 4: time when [C5 H6 ]t = (0.20)[C5 H6 ]0

3: [C5 H6 ]300 x = t; y =
[C5 H6 ]t 1
t= x = 612 s
1 (0.20)(0.0400)
300y =
[C5 H6 ]300
1
[C5 H6 ]300 = = 0.0135 M
300y
Half-Life t1/2
- time required to reduce the concentration of the reactant to half of its initial value

1
t = t1 /2 when [A]t = [A]0
2
ln[A]t = kt + ln[A]0
[A]t = kt + [A]0
1
1 ln [A]0 = kt 12 + ln[A]0
[A]0 = kt 12 + [A]0 2
2
1 1
kt 12 = [A]0 [A]0 kt 12 = ln[A]0 ln [A]0
2 2
n = 0: kt 1 = 1 [A] n = 1: [A]0
2 2
0 kt 12 = ln 1
2 [A]0
[A]0
t 12 = ln 2
2k t 12 =
k
t 12 [A]
t 12 independent of [A]
1 1 [A]0
= kt +
[A]t [A]0 n = 0 : t 12 =
1 1
2k
1 = kt 12 +
[A]0
ln 2
2 [A] 0 n = 1 : t 12 =
2 1 k
= kt 12 1
[A]0 [A]0 n = 2 : t 21 =
n = 2: 1 k[A]0
= kt 12
[A]0
1 20 s 1 10 s 1 5s 1
n = 0 : 1M M
t 12 = M M
k[A]0 2 4 8
20 s 1 20 s 1 20 s 1
n = 1 : 1M M M M
2 4 8
1 20 s 1 40 s 1 80 s 1
t 12 n = 2 : 1M M M M
[A] 2 4 8
Examples:
1. Given: order = 1 t 12 = 12.0min

12 min 12 min 12 min 12 min
100% 50% 25% 12.5% 6.25%
a. 25% remaining: t = 12+12 = 24 min
b. 20% remaining: [A]t = 0.20[A]0
ln 2
ln[A]t = kt + ln[A]0 t 12 =
k
ln 2
k= = 0.0578 min1
12.0 min
ln(0.20)[A]0 = (0.0578 min1 )t + [A]0

(0.20)[A]0
ln = (0.0578 min1 )t
[A]0
ln (0.20)[A]
[A]0
0
t= = 27.84 min
(0.0578 min1 )
c. 10% remaining: [A]t = 0.10[A]0
[A]t
ln = kt
[A]0
(0.10)[A]0
ln = (0.0578 min1 )t
[A]0
ln (0.10)[A]
[A]0
0
t= = 39.84 min
(0.0578 min1 )

1 1
2. Given: order = 2 HI(g) H2(g) + I2(g)
2 2
t=5 [A]0 = 0.90 M [A]5 = 0.68 M
a. time when [HI] = 0.50 M
1 1
= kt +
[HI]t [HI]0
1 1
= 5k +
0.68 M 0.90 M
1
0.901 M
k = 0.68 M = 0.0719 M 1 min1
5 min
1 1
= (0.0719 M 1 min1 )t +
0.50 M 0.90 M
1 1
0.50 M 0.90 M
t= = 12.36 min
(0.0719 M 1 min1 )
b. half-life when [HI] is 0.90 M
1 1
t 21 = =
k[A]0 (0.0719 M min1 )(0.90 M )
1
t 12 = 15.45 min
Gas-Phase Reactions
A(g) B(g) + 2C(g)

A B C
PT OT AL = PA + PB + PC
t=0 PA,0 0 0
C -x +x +2x = PA,0 x + x + 2x
t PA,0 -x x 2x = PA,0 + 2x 2

[A]t
n=1 ln = kt
[A]0
P
from PV = nRT, P = MRT, C =
RT
Therefore,
PA,t
RT
ln PA,0
= kt
RT
PA,t
ln = kt
PA,0
Example:
Given: n=1 C8 H18 O2(g) 2C3 H6 O(g) + C2 H6(g)

t 12 at 147 C = 80 min PA,0 = 800 mmHg PA,600 =?
PA,t ln 2
ln = kt t 12 =
PA,0 k
ln 2 ln 2
k= = = 0.0087 min1
t 12 80 min
PA,t
ln = (0.0087 min1 )(600 min)
800 mmHg
min1 )(600 min)
PA,t = (e(0.0087 )(800 mmHg) = 4.43 mmHg

C8 H18 O2(g) C3 H6 O(g) C2 H6(g)
t=0 800 mmHg 0 0
C -x +2x +x
t 4.43 mmHg 2x x
800 x = 4.43 mmHg

x = 795.57 mmHg
PT OT AL = 4.43 + 2x + x
PT OT AL = 4.43 + 2(795.57) + 795.57 = 2391.14 mmHg
4. Temperature Temperature, Rate

- increasing the temperature increases the initial energy of the reactants, making it easier
to overcome the activation energy
- the temperature alters the rate constant T, k
Ea
Arrhenius Equation: k = Ae RT
Ea : activation energy T: absolute tempterature (in K)

R: ideal gas constant (8.314 J/molK) A: pre-exponential factor
Ea
k = Ae RT
Ea
ln k = ln A + ln e RT
Ea 1
ln k =
+
ln A Ea 1
R T ln k2 = R T2 + ln A
y b Ea 1
mx ln k1 = R T1 + ln A
1 ln kk21 = Ea
R T12 T11
Plot ln k vs
T y2 y1 = m(x2 x1 )

Ea
slope =
R
y-int = ln A
Example:
T ( C) 0 25 35 45
k(s1 ) 103 0.0106 0.319 0.986 2.92
Find Ea and A:
Ea 1 1
ln k = + ln A Plot ln k vs r = 0.999
R T T
Ea y int = ln A = 28.336
slope = = 10863
R A = 2.02 1012
E a = 90319 J
1
Find half-life at 40 C: x = y = ln k
T
ln 2
1 t 12 =
ln k = y k
313.15 ln 2
ln k = 6.355 =
1.738 103 s1
k = 1.738 103 s1 = 399 s

Quiz
Given: n=2
Ea = 250 kJ/mol [N2 O]t = 0.20[N2 O]0 = 0.002 M [N2 O]0 = 0.01 M
T1 = 838.15 K t 12 = 25.25 hours k1 =?
T2 = 973.15 K t =? k2 =?
1 1 1
= kt + t 12 =
[N2 O]t [N2 O]0 k1 [N2 O]0
1 1
k1 = = = 3.96 M 1 hr1
(t 12 )([N2 O]0 ) (25.25 hours)(0.01 M )

k2 Ea 1 1
ln =
k1 R T2 T1

k2 250000 J/mol 1 1
ln = J

3.96 M 1 hr1 8.314 molK 973.15 838.15
k2
= 145.03
3.96 M 1 hr1
k2 = 574.32 M 1 hr1
1 1
= kt +
[N2 O]t [N2 O]0
1 1
= (574.32 M 1 hr1 )t +
0.002 M 0.01 M
t = 0.696 hrs or 41.79 min
5. Catalyst
- substance that is not consumed in the reaction
- alters the activation energy
1. positive catalyst: speeds up the reaction by lowering the activation energy
2. negative catalyst: inhibitor: slows down the reaction by increasing the
activation energy
a. homogenous catalyst: catalyst in the same phase as the reactants

- it provides an alternate pathway with a series of steps with a lower
activation energy each
- changes the reaction mechanism
- intermediate: species formed at one step but consumed at subsequent steps
Overall Reaction: 2H2 O2 2H2 O + O2 I : Catalyst

H2 O2 + I H2 O + OI
OI : Intermediate
H2 O2 + OI H2 O + O2 + I
2H2 O2 2H2 O + O2
Uncatalyzed Reaction Catalyzed Reaction

Higher activation energy than catalyzed Each step has lower activation energy than
the uncatalyzed
Has only one transition state Has one transition state for each step
Has no intermediate Has one or more intermediates
same change in enthalpy

Transition State Intermediate
Peaks in the energy profile Valleys in the energy profile
high energy, cannot be analyzed lower energy, can be analyzed
b. heterogenous catalyst: catalyst in the different phase as the reactants

- usually solid
- acts through adsorption - through binding sites in the solid's surface
Pt
Example: CH2 = CH2 + H2 C2 H6
Reaction Mechanisms
- detailed description of how a reaction occurs
- shows the reason why the observed rate orders are different from the coefficient in the
balanced equation
Overall Reaction: CO + NO2 CO2 + NO Rate = k [NO2 ]2

1 k
NO2 + NO2 NO3 + NO (slow)
k2
CO + NO3 CO2 + NO2 (fast)
CO + NO2 CO2 + NO
elementary steps - the most basic steps

- the orders of reaction are the coefficients in the equation
slowest step - rate determining step

- rate law of reaction = rate law of slowest step
Rate = k1 [N O2 ]2
molecularity 1: unimolecular concerted reactions: single step

2: bimolecular
3: termolecular
Concerted Reaction:
CH3 Cl + OH CH3 OH + Cl
Rate = k[CH3 Cl][OH ]
- you can never tell with absolute certainty the exact mechanism of a reaction, you can
only propose plausible mechanisms
Requirements for a Plausible Proposal:

1. Sum of elementary steps = overall reaction
2. Rate law for the mechanism = observed rate law
Example 1:
Overall Reaction: 2NO + Cl2 2NOCl Rate = k[NO]2 [Cl2 ]
Mechanism 1
k1
NO + Cl2 NOCl2 (slow)
k2
NO + NOCl2 2NOCl (fast)
2NO + Cl2 2NOCl
Step 1 is the rate determining step: Rate = k1 [N O][Cl2 ]

The proposed mechanism is not plausible

Mechanism 2
NO + Cl2 NOCl2 (fast)
NO + NOCl2 2NOCl (slow)
2NO + Cl2 2NOCl
Rate = [N O][N OCl2 ]
Methods for Eliminating Intermediates

1. Equilibrium Method
- since fast steps are faster than the slowest step, they will become in equilibrium before
the slowest step finishes
N O + Cl2 N OCl2
[N OCl2 ]
K= [N OCl2 ] = K[N O][Cl2 ]
[N O][Cl2 ]
Rate = k2 K[N O]2 [Cl2 ] = k[N O]2 [Cl2 ]

The proposed mechanism is plausible
2. Steady State Approximation

- the intermediate will reach a steady state before the reaction finishes
d[int] d[int] d[int]

=0 =0
dt dt appearance dt disappearance
Rate of appearance of NOCl2 = Rate of disappearance of NOCl2
k1 [N O][Cl2 ] = k1 [N OCl2 ] + k2 [N O][N OCl2 ]

k1 [N O][Cl2 ] = [N OCl2 ](k1 + k2 [N O])
k1 [N O][Cl2 ]
[N OCl2 ] =
k1 + k2 [N O]
k2 k1 [N O]2 [Cl2 ]
Rate =
k1 + k2 [N O]
If k1 >>> k2 k1 + k2 [N O] k1
k2 k1 [N O]2 [Cl2 ] k2 k 1
Rate = = [N O]2 [Cl2 ]
k1 k1
Holds with experimental rate law
If k2 >>> k1 k1 + k2 [N O] k2 [N O]
k2 k1 [N O]2 [Cl2 ]
Rate = = k1 [N O][Cl2 ]
k2 [N O]
Does not hold with experimental rate law
This means that rate2 < rate1
Example 2:
Overall Reaction: A + 2B C Rate = k[A]2 [B]
A+A A2 (fast)
A2 + B AB + A (slow)
AB + B C (fast)
A + 2B C
Rate = k2 [A2 ][B]

Equilibrium Method:
[A2 ]
K= [A2 ] = K[A]2
[A]2
Rate = k2 [B]K[A]2
Rate = k2 K[A]2 [B]
The proposed mechanism is plausible
k1 [A]2 = k1 [A2 ] + k2 [B][A2 ]

k1 [A]2 = [A2 ](k1 + k2 [B])
k1 [A]2
[A2 ] =
k1 + k2 [B]
k2 k1 [A]2 [B]
Rate =
k1 + k2 [B]
If k1 >>> k2 k1 + k2 [B] k1
k2 k1 [A]2 [B] k 2 k1 2
Rate = = [A] [B]
k1 k1
Holds with experimental rate law
If k2 >>> k1 k1 + k2 [B] k2 [B]
k2 k1 [A]2 [B]
Rate = = k1 [A]2
k2 [B]
Does not hold with experimental rate law
This means that rate2 < rate1
Chain Reaction / Mechanism

- occurs at high temperatures or at presence of radiation
Example:

H2 + Br2 2HBr
1. Chain initiation: Br2 + light 2Br radical: with unpaired electron

2. Chain propagation: Br +H2 HBr + H they are reactive
H +Br2 HBr + Br ...
3. Chain termination: Br +Br Br2
H +H H2
Br +H HBr
Overall Reaction: propagation steps:

Br +H2 HBr + H
H +Br2 HBr + Br
H2 +Br2 2HBr

CF2 Cl2 + uv CF2 Cl + Cl (chain initiation)

Cl + O3 O2 + ClO (chain propagation)
ClO + O O2 + Cl (chain propagation)
O3 + O 2O2

Quiz
Overall Reaction: I + OCl OI + Cl
OCl + H2 O HOCl + OH (fast)

I + HOCl HOI + Cl (slow)
HOI + OH H2 O + OI (fast)
I + OCl OI + Cl
Equilibrium Method:
[HOCl][OH ] K[OCl ]
K= [HOCl] =
[OCl ] [OH ]
Rate = k2 K[I ][OCl ][OH ]1

Rate = k[I ][OCl ][OH ]1
Steady State Approximation

k1 [OCl ]
k1 [OCl ] = k1 [HOCl][OH ] + k2 [I ][HOCl] [HOCl] =
k1 [OH ] + k2 [I ]
k2 k1 [I ][OCl ]
Rate =
k1 [OH ] + k2 [I ]
k2 k1
If k1 >>> k2 , Rate = [I ][OCl ][OH ]1
k1
If k2 >>> k1 , Rate = k1 [OCl ]
Nuclear Chemistry
Chemical Reactions Nuclear Reactions
transformation of the nu-
Change that occurs formation/breaking of bonds
cleus itself
Subatomic Particles Involved valence electrons all subatomic particles
Energy change lower higher
Radioactivity: Henri Bequerel

- spontaneous emission/radiation of particles in
order to become stable
- radioactive nuclei: radionuclide
- spontaneous: occurs naturally
Stability
- atoms with low atomic number: n/p ratio is 1:1
- atomic numbers have higher p-p repulsion so
they need more neutrons to overcome
that repulsion
- atoms without 1:1 ratio are unstable and outside
the belt of stability
- largest atom with a 1:1 ratio is 83Bi
Balancing Nuclear Reactions

A
A: mass #: p + n (nucleons)
ZX
Z: atomic #: p
- balance both A and Z in nuclear reactions
14 4 17 1
Example: 7 N +2 He 8 O +1 H

0
proton: 11 p or 11 H electron: 1 e neutron: 10 n
Type of Nuclear Reactions

1. Radioactive Decay: spontaneous emission of radiation/particles
a. Alpha Decay: occurs usually on heavy atoms (Z>82)
4 4
Alpha Particle: 2 He or 2
238 234 4
Example: 92 U 90 T h +2 He
b. Beta Decay: done by nuclei with high n/p ratio p, n, n\p ratio
0 0
Beta Particle: 1 e or 1
234 234 0 1 1 0
Example: 90 U 91 P a +1 e 0 n 1 p +1 e
c. Gamma Decay: electromagnetic radiation (light), usually accompanies other decays

0
Gamma Particle: 0
- the above three decays are ionizing radiation and are harmful
Material Alpha passes? Beta passes? Gamma passes?
Paper NO YES YES
Wood NO NO YES
Concrete/Lead NO NO SOME
- differences are due to different masses and charges of ionizing radiation
d. Positron emission: done by nuclei with low n/p ratio

p, n, n\p ratio
30 30 0 1
Example: 15 P 14 Si +1 e 1p 10 n +01 e
e. Electron capture: done by nuclei with low n/p ratio

p, n, n\p ratio
40 0 40 1
Example: 19 K +1 e 18 Ar 1p +01 e 10 n
Radioactive Disintegration Series

- after one instance of decay, a nucleus can still undergo decay
238 234 234 234 230 206

Example: 92 U 90 T h 91 U 92 U 90 T h 82 P b
236 207 232 208

92 U 82 P b 92 U 82 P b
Kinetics of Radioactive Decay

- all obey first-order kinetics
Activity = kN
SI unit: disintegration per second (dps) / Bequerel (Bq)
Other unit: Curie (Ci): activity of 1 gram of radium
1 Ci = 3.7x1010 Bq

Nt ln 2
Integrated Rate Law: ln = kt Half Life: t 12 =
N 0 k

Example:
t 12 = 12.8 hrs N = 1.50 mg t = 48 hrs

ln 2 1g 1 mol 6.02 1023 disintegrations 1 hr
activity = kN = (mg)
t 12 1000 mg 64 g 1 mol 3600 s
23

ln 2 1g 1 mol 6.02 10 disintegrations 1 hr
= (1.50 mg)
12.8 hrs 1000 mg 64 g 1 mol 3600 s

1 Ci
= 2.12 101 4 Bq = 5741 Ci
3.7 1010 Bq
Nt
ln = kt
N0
Nt = ekt (N0 )
hr 1 )(48 hrs)
Nt = e(0.0542 (1.50 mg) = 0.111 mg = 1.11 104 g
Mass Defect
- calculated mass of nucleons in a nucleus is always greater than the actual mass
- the mass is transformed into nuclear binding energy
- energy that is released when nucleons combine
- energy that is required to separate the nucleons
- also a measure of stability of a nucleus
- NBE Stability; the nucleus is more intact
Example
28
14 Si atomic mass = 27.96924

1.00728 amu 1.00867 amu
atomic mass = 14 protons + 14 neutrons = 28.22330 amu
proton neutron
m = calculated mass - actual mass = 28.22330 amu 27.96294 amu
m = 0.25406 amu
E = mc2

1g 1 kg
E = (0.25406 amu)(3 108 )2 = 3.798 1011 J
6.02 1023 amu 1000 g
3.798 1011 J
nuclear binding energy per nucleon = = 1.357 1012 J/nucleon
28 nucleons
Quiz
activity0 = 0.0500 Ci activityt = 0.0310 Ci t = 30.0 hrs

Nt
ln = kt
N0
activityt
ln k
activity0
0.0310 Ci
ln 0=0.0500
k Ci
k= =
t 30.0 hrs
k = 0.159 hr1
ln 2
t 12 =
k
ln 2 ln 2
t 12 = = = 43.5 hours
k 0.159 hr1
Nt
N96 : ln = (0.159 hr1 )(96 hours) = 1.5624
N0
Nt
= 0.2166 remaining 78.34% disintegrated
N0
56
26 F e atomic mass = 55.92066

1.00728 amu 1.00867 amu
atomic mass = 26 protons + 30 neutrons = 56.44938 amu
proton neutron
m = calculated mass - actual mass = 56.44938 amu 55.92066 amu
m = 0.52872 amu
E = mc2

1g 1 kg
E = (0.52872 amu)(3 108 )2 = 7.904 1011 J
6.02 1023 amu 1000 g
7.904 1011 J
nuclear binding energy per nucleon = = 1.41 1012 J/nucleon
56 nucleons
2. Nuclear Transmutation: bombardment of a nucleus by a particle to form another nucleus

14
Examples: 7 N +42 He 17 1
8 O +1 H
9
4 Be +42 He 12 1
6 C +0 n
Short-Hand: bombarded (bombarder, new particle) new nucleus

14 17 9 12
Example: 7 N (, p) 8 O 4 Be (, n) 6 C
Transuranium Elements
- man-made elements, prepared from Uranium
- located after Uranium in the periodic table

238 239
Example: 1st Transuranium element to be discovered: 92 U (n, ) 93 N p

238 1 239 0
92 U +0 n 93 N p +1 e
3. Nuclear Fission: splitting of a heavy nucleus to form two lighter nuclei

235
92 U +10 n 142
56 Ba +91 1
36 Kr + 30 n
Nuclear Chain Reaction

- when a particle product from a previous fission is used to do another one

- critical mass: minimum mass needed to sustain a nuclear chain reaction
4. Nuclear Fusion: combining of two light nuclei to form a heavier nucleus

- produces a higher energy, no radioactive waste
- hard form of energy to manipulate
411 H + 201 e 4
2 He
Effect of Radiation on Biological Matter

- ionizing radiation can rip off electrons
radiation
H2 O H2 O+ + e
OH starts a chain reaction that affects cells
H2 O+ + H2 O H3 O+ + OH
SI Unit Other Unit Conversion Factor

Activity Bequerel (Bq) Curie (Ci) 1 Ci = 3.7x1010 Bq
Absorbed Dose Gray (Gy) in J/kg rad in 0.01 J/kg 1 Gy = 100 rad
Effective Dose Sievert(Sv) Gy x RBE rem rad x RBE 1 Sv = 100 rem
Example
mass = 75 kg Activity = 90 mCi time = 2 hours

13
energy = 9.1210 J/disintegration 85% absorbed RBE = 1

1 Ci 3.7 1010 Bq
Activity in Bq = 90 mCi = 3.3 109 Bq
1000 mCi 1 Ci

3.3109 disintegrations 9.121013 J
1 s (7200 s) 1disintegration (0.85)
Absorbed Dose = = 0.246 Gy
75 kg

100 rad
0.246 Gy = 24.6 rad
1 Gy
Absorbed Dose = Gy x RBE = 0.246Gy 1 = 0.246 Sv

100 rem 1000 mrem
0.246 Sv = 24600 mrem
1 Sv 1 rem
Chemical Thermodynamics
- branch of chemistry that deals with heat/energy changes
- predicts the spontaneity of a reaction
System: part of the universe under study

Surroundings: everything not in the system
System + Surroundings = Universe
Types of System
1. Open - allows the exchange of matter and energy
- nonconservative system
- the wall is permeable and diathermal; imaginary wall
2. Closed - only allows the exchange of energy

- conservative to matter, nonconservative to energy
- the wall is impermeable and diathermal; real wall
3. Isolated - does not allow the exchange of both matter and energy
- conservative system
- the wall is impermeable and adiabatic; real wall
Properties of the System
1. Extensive - properties that are dependent on the amount of matter present
Examples: mass, weight, volume, moles
2. Intensive - properties that are independent on the amount of matter present
Examples: temperature, density, molar mass, boiling point
Extensive Property 1
Intensive Property =
Extensive Property 2
Extsys = Ext1 + Ext2 + . . .

Intsys = Int1 = Int2 = . . .
State Function
- properties that define the state of the system
- they are path independent and only focus on the initial and final states of the system
Examples: P, V, T, U, H, G, S
Nonstate Function
- properties that are dependent on the path taken by the system
Examples: q and w
Example: travelling from QC to UPM paths: jeep, FX, taxi distance is constant
distance is the state function fare is the nonstate function
Sign Conventions
(+) q = heat is absorbed by the system (-) q = heat is released by the system
(+) w = work is done on the system (-) w = work is done by the system
Note, in Chemistry, work is defined as the Pressure-Volume work (compression/expansion)
Heat, q (+) q = heat is absorbed by the system

(-) q = heat is released by the system
q = mcT m: mass c: specific heat

- the amount of heat needed to raise the
temperature of 1 gram of substance by 1C
- H2O: 1cal/gC or 4.184 J/gC
q = nCT n: moles C: molar heat capacity

- the amount of heat needed to raise the
temperature of 1 mole of substance by 1C
- c and C are interconvertible
For Ideal Gases: CV = C at constant Volume

CP = C at constant Pressure
- this is because gases are greatly affected by pressure changes and are compressible
- liquids and solids are incompressible and therefore their CV and CP are very close
monoatomic diatomic
3 5
CV R R
2 2
5 7
CP R R
2 2
C P = CV + R
Work, w (+) w = work is done on the system
(-) w = work is done by the system
F
P-V work: P = F = PA A: cross-sectional area
w = F dx A
A dx = dV P: external pressure

w = P dV Following the sign convention: w = P dV = F dx = P dV

- the negative sign is added to follow direction, it has no bearing on the magnitude
Two Types of Work

wirrev = Pext dV
Irreversible Work - actual work that we do
Irreversible Work
Single-Step: from V1 to V2 in one pressure change
Two-Step: from V1 to V2 in two pressure changes
Three-Step: from V1 to V2 in three pressure changes
and so on....
Reversible Work
Infinite Steps: from V1 to V2 in infinite pressure changes
Work in One-Step < Work in Two-Step < Work in Three-Step < < Work in Infinite-Step
Reversible Work - maximum work that the system can perform during expansion
- minimum work that the system can perform during compression

- gradual expansion, infinitesimal change, infinite time is required
wrev = Pgas dV
- therefore, can be easily reversible by also applying
infinitesimal pressure compared to irreversible work
First Law of Thermodynamics (Law of Conservation of Energy)

- the energy of the whole universe is constant
U: internal energy - total energy of the system (all potential, kinetic, etc. energy)
U is the focus of this law: a change in the system is transferred to the surroundings
2 ways of transferring energy: heat and work
U = q + w

Ideal Gas Systems (dependent on path)

1. Isobaric (Constant Pressure)
qP = nCP T U = q + w

= nCP T nRT
wirrev = Pext dV
= n(CP R)T
V2 = nCV T
wrev = Pgas dV = Pgas dV
V1
= P V = nRT
2. Isocoric (Constant Volume)
qV = nCV T U = q + w
wirrev = 0 =q
wrev = 0 = nCV T

3. Isothermal (Constant T)

U = 0
wirrev = Pext dV
U = q + w
0=q+w wrev = Pgas dV
q = w

V2
nRT
= dV
V
V1
V2
dV
= nRT
V
V1
V2
= nRT ln
V1
4. Adiabatic

q=0
U = q + w
U = w
U = nCV T
Example
Given:
Helium Gas n = 3 moles Tf = 100 K Ti = 25 K
wrev =? q=? U=? Assume He is an ideal gas
A: at constant P
qP = nCP T

5 J
qP = (3 mol) 8.314 (100K 25K)
2 molK
qP = 4676.63 J
V2 U = q + w
wrev = Pgas dV
U = 4676.63 J + 1870.65 J
V1
U = 2805.98 J
V2
wrev = Pgas dV = P V = nRT
U = nCV T
V1
3 J
J U = (3 moles) 8.314 (75K)
wrev = (3 moles) 8.314 (75K) 2 molK
molK
wrev = 1870 J U = 2805.98 J

B: at constant V
wrev = 0 U = q + w
qV = nCV T U = q + 0 = q
U = 2805.98 J
3 J
qV = (3 mol) 8.314 (100K 25K)
2 molK
qV = 2805.98 J

For Isobaric Systems, qP is called H
U = qp + w Isocoric: H = U + (P V )
U = H + w = nCV T + nRT
H = U w = n(CV + R)T
H = U (P V ) = nCP T
H = U + P V
Isothermal: H = 0
H: enthalpy = U + P V
Adiabatic: H = nCP T
For Ideal Gases: H = nCP T
Example:
Given:
N2(g) n = 2 moles Vf = 4L Vi = 2L
Assume N2(g) is ideal T = 303.15 K
A: reversible
H = 0 U = 0 (isothermal system)
V2 V2
nRT
wrev = Pgas dV = dV
V
V1 V1
V2
dV V2
wrev = nRT = nRT ln
V V1
V1
J 4L
wrev = (2moles)(8.314 )(303.15K) ln
molK 2L
wrev = 3494 J
q = w
q = 3494 J
B: against a constant pressure of 2 atm (irreversible)

H = 0 U = 0 (isothermal system)
V2 V2
wirrev = Pext dV = Pext dV
V1 V1
wirrev = Pext (V2 V1 )

wirrev = (2atm)(4L 2L)
J
8.314 molK
wirrev = 4 Latm Latm
= 405.26 J
0.08206 molK
q = w
q = 405.26 J
Isobaric Isocoric Isothermal Adiabatic

q qP = nCP T qV = nCV T q = w 0

wirrev Pext dV 0 Pext dV Pext dV


V2
wrev P V = nRT 0 nRT ln Pgas dV
V1
U nCV T nCV T 0 w = nCV T
H nCP T nCP T 0 nCP T
Quiz
Given:
O2(g) n = 2 moles T1 = 313.15 K
adiabatic (q=0) Pgas = 4.50 atm Pext = 800 torr
V2 V2
wirrev = Pext dV = Pext dV
nRT
V1 V1 V1 =
P
wirrev = Pext (V2 V1 ) Latm
2 mol 0.08206 molK 313.15K
1 atm V1 =
wirrev = 800 torr (34.26L 11.42L) 4.50 atm
760 torr V1 = 11.42L
J
8.314 molK
wirrev = 24.04 Latm Latm
= 2435.85 J
0.08206 molK V = 3V = 3(11.42L)
2 1
V2 = 34.26L
U = q + w = 0 + w = w
U = 2435.85 J
U = nCV T

5 J
2435.85 J = (2 mol) 8.314 (T2 313.15 K)
2 molK
T2 = 254.55 K
Thermochemistry
- measurement and calculation of heats of reaction at constant pressure
- H is measured
endothermic: H > 0
H = qP H = U + PV H = U + (P V )
exothermic: H < 0
Hrxn = Urxn + ng RT
ng = moles of gaseous products - moles of gaseous reactants
Example
Given:
U = -2648 kJ/mol T = 298.15 K 13 5
13 ng = 4 =
C4 H10(l) + O2(g) 4CO2(g) + 5H2 O(l) 2 2
2
Hrxn = Urxn + ng RT

kJ 5 J 1 kJ
Hrxn = 2648 + 8.314 (298.15 K)
mol 2 molK 1000 J
kJ
Hrxn = 2654.20
mol

Evaluating H
1. Calorimetry
- apparatus used to measure heat: isolated vessel
a. Bomb (Constant V) Calorimeter: qV (U)
b. Constant Pressure Calorimeter: qP (H)
qtotal = 0
qrxn + qcal = 0 (dependent on system)
qcal = mcT
= Ccal T (m and c are constant - Ccal : Calorimeter Constant)
Finding which exchanged heat to create the working equation
Finding Ccal :
qhot H2 O + qtap H2 O + qcal = 0
Finding qf us of ice:
qf us + qice H2 O + qtap H2 O + qcal = 0
Finding qneutralization :
qneut + qacid + qbase + qcal = 0
Example:
Given:
Phenol (C6 H5 OH(s) ) m = 1.800 g Ccal = 11.66 kJ/ C
Bomb Calorimeter T1 = 21.36 C T2 = 26.37 C
qtotal = 0
qcombustion + qcal = 0
qcombustion = qcal = Ccal T
qcombustion = qV = 58.42 kJ per 1.8 g phenol

58.42 kJ 94.12 g
U =
1.8 g 1 mol
kJ
U = 3054.72
mol
H = U + ng RT C6 H5 OH(s) + 7O2(g) 6CO2(g) + 3H2 O(l)

average temp: 298.15 K ng = 6 7 = 1

kJ J 1 kJ
H = 3054.72 + (1) 8.314 (298.15 K)
mol molK 1000 J
kJ
H = 3057.20
mol
2. Standard Heat of Formation (Hf)

- heat involved in the formation of 1 mole of compound from its elements
at standard state (P = 1 atm; activity = 1)

1 kJ
2C(s, graphite) + 3H2(g) + O2(g) C2 H5 OH(l) Hf = 277.7
2 mol
kJ
Ca(s) + Cl2(g) CaCl2(s) Hf = 795.8
mol
3 kJ
N2(g) + 2H2(g) + O2(g) N H4 N O3(g) Hf = 365.6
2 mol

Hf, elements = 0

Hf, N2(g) = 0

Hf, O2(g) =0

Hf, Cl2(g) =0

Hf, Br2(g) = 0 (is not a gas in standard state; liquid)

Hf, Cgraphite = 0 (stable allotrope in standard state)

Hf, Cdiamond = 0
Hrxn = nHf , products nHf , reactants
Example
13
C4 H10(g) + O2(g) 4CO2(g) + 5H2 O(l)
2

kJ kJ
= (4 mol) 393.5 + (5 mol) 285.83
mol mol

kJ 13 kJ
(1 mol) 124.73 +( mol) 0
mol 2 mol
= 2878.42kJ
3. Hess' Law of Heat Summation

- possible because H is a state function

A B H1
B C H2
C D H3
A D H = H1 + H2 + H3
solid liquid Hf us
liquid gas Hvap
solid gas Hsub
Hsub = Hf us + Hvap
Example
kJ
4N H3(g) + 3O2(g) 2N 2(g) + 6H2 O(l) H = 1531
mol
kJ
N2 O(g) + H2(g) N 2(g) + H2 O(g) H = 367.4
mol
1 kJ
H2(g) + O2(g) H2 O(l) H = 285.9
2 mol

1 1 kJ
[4N H3(g) + 3O2(g) 2N 2(g) + 6H2 O(l) ] H = 1531
2 2 mol
kJ
3[N2 O(g) + H2(g) N 2(g) + H2 O(g) ] H = 3 367.4
mol
1 kJ
3[H2(g) + O2(g) H2 O(l) ] H = 3 285.9
2 mol
Overall : 2N H3(g) + 3N2 O(g) 4N 2(g) + 3H2 O(l)

kJ kJ kJ
HT = 1531 367.4 285.9 = 1010 kJ
mol mol mol
4. Bond Enthalpy
- energy required to break 1 mol of a bond
- applicable only to gaseous covalent compounds
- correlated to atomic size and bond length
- bond enthalpy double bond is not equal to twice for that of a single bond
- different nature of bonds (single: sigma, double: sigma + pi)
Hrxn = nH, bonds broken nH, bonds f ormed
Example:
13
C4 H10(g) + O2(g) 4CO2(g) + 5H2 O(g)
2
Using Standard Heats of Formation:


kJ kJ
= (4 mol) 393.5 + (5 mol) 285.83
mol mol

kJ 13 kJ
(1 mol) 124.73 +( mol) 0
mol 2 mol
= 2878.42kJ
Using Bond Enthalpies:

Hrxn = nHf , bonds broken nHf , bonds f ormed

kJ kJ 13 kJ
= (10 mol) 413 + (3 mol) 348 +( mol) 495
mol mol 2 mol

kJ kJ
(8 mol) 799 + (10 mol) 463
mol mol
= 2630.5kJ
C4 H10(g) + 13
2 O2(g) 4CO2(g) + 5H2 O(g) H = 2630.5 kJ
5H2 O(g) 5H2 O(l) H = 5(44.01 kJ)
C4 H10(g) + 13
2 O2(g) 4CO2(g) + 5H2 O(l) H = 2850.55 kJ
Measuring Hrxn using standard heats of formation is more reliable than using bond enthalp-
ies since bond enthalpies change according to the environment of the bond.
Quiz
Given:
C8 H18 V = 10.00 mL = 0.688 g/mL Ccal = 7.62 kJ/ C
T2 = 66.5 C T1 = 23.2 C Average = 25 C Bomb Calorimeter

qtotal = 0
qcomb + qcal = 0
qcomb = qcal
= Ccal T

kJ
7.62 (66.5 C 23.2 C)
C
= 329.946 kJ = qv
329.946 kJ kJ
U = 0.688 g 1 mol = 5467.21 mol
(10.00 mL) 1 mL 114 gC H
8 18
25 25 9
C8 H18(g) +O2(g) 8CO2(g) + 9H2 O(l) ng = 8 =
2 2 2
H = U + ng RT

kJ 9 kJ
= 5467.21 8.314 103 (298.15 K)
mol 2 molK
kJ
= 5478.36
mol

kJ kJ kJ
5478.36 = (8 mol) 393.5 + (9 mol) 285.83
mol mol mol

13 kJ
(1 mol) Hf, C8 H18 + ( mol) 0
2 mol
kJ
Hf, C8 H18 = 242.11
mol
Second Law of Thermodynamics

- enables us to predict the driving force of reactions
- spontaneous: naturally occuring
Examples: rusting, transfer from hot to cold
- the second law predicts the direction of a spontaneous processs
S: entropy
- measure of the degree of disorder or randomness
dqrev
dS =
T
- the natural tendency of things is to obtain disorder

- the entropy od an isolated system increases in a spontaneous process
- as long as the system absorbs heat, dS
- a system with more entropy is more probable
S>0 S>0 S<0 S<0
solid liquid gas liquid solid
- being an isolated system is important (no exchange between system and surroundings)
- we can treat the whole universe as an isolated system
Spontaneous: increase in dS of universe Suniverse > 0

Ssys + Ssurr > 0

Ideal Gas System
1. Isobaric 2. Isocoric
dqP nCP dT dqV nCV dT

dS = = dS = =
T T T T
S 2 T 2 S 2 T 2
nCP dT nCV dT
dS = dS =
T T
S1 T1 S1 T1
T2 T2
S = nCP ln S = nCV ln
T1 T1
3. Isothermal 4. Adiabatic
dqrev dwrev dS = 0
dS = =
T T
(Pgas dV ) Pgas dV
= =
T T
nRT
dV dV
= V = nR
T V
S2 S2
dV
S = nR
V
S1 S1
V2
S = nR ln
V1
Phase Changes (constant T and constant P)
qrev Htransition
S = =
T Ttransition
Chemical Reactions

Srxn = nSprod nSreac

Selements = 0
Example
Given:
H2 O(s) H2 O(g) n = 2 moles Tf = 383.15 K Ti = 268.15 K
P = 1 atm
Hf us, ice = 6.02 kJ/mol Hvap, water = 40.67 kJ/mol
ice CP = 37.7 J/molK
liquid water CP = 75.3 J/molK
steam CP = 33.9 J/molK

T2 J 273.15 K
S1 = nCP ln = (2 mol) 37.7 ln
T1 molK 268.15 K
J
= 1.39
K

kJ

nHf us (2 mol) 6.02 mol
S2 = =
Tm 273.15 K
J
= 44.08
K
T2 J 373.15 K
S3 = nCP ln = (2 mol) 75.3 ln
T1 molK 273.15 K
J
= 46.98
K
kJ
nHvap (2 mol) 40.67 mol
S4 = =
Tb 373.15 K
J
= 217.98
K
T2 J 383.15 K
S5 = nCP ln = (2 mol) 33.9 ln
T1 molK 373.15 K
J
= 1.79
K
ST = S1 + S2 + S3 + S4 + S5
J
= 312.22
K
Quiz
Given:
Hf us = 9.87 kJ/mol Hvap = 30.7 kJ/mol Svap = 86.9 J/molK
liquid CP = 136.1 J/molK
gas CP = 84.67 J/molK
Ti = 278.75K
J
Hvap Hvap 30700 mol
Svap = Tb = = J
= 353.28 K
Tb Svap 86.9 molK
ST = S1 + S2 + S3 + S4
J
9870 mol J 353.28 K J J 373.15 K
= + 136.1 ln + 86.9 + 86.67 ln
278.75 K molK 278.75 K molK molK 353.28 K
J
= 159.19
molK
Alternative Basis for Spontaneity
Suniverse > 0
Ssystem + Ssystem >0
qsys
Ssys >0
T
T Ssys qsys >0
at constant P, qP = H T Ssys Hsys >0
Hsys T Ssys <0
Gsys <0
G: Gibb's Free Energy

- available energy needed to do useful work
G= H

TS G = H T S
heat available heat used

G < 0: spontaneous G = 0: equilibrium G > 0: nonspontaneous
Example:
Hf us 6.02 kJ/mol
Hf us = 6.02 kJ/mol Sf us = =
Tm 273.15 K
kJ
= 0.02204
molK
G = H T S

kJ kJ kJ
at 0 C : G = 6.02 (273.15K) 0.02204 =0
mol molK mol
EQUILIBRIUM at 0

kJ kJ kJ
at 10 C : G = 6.02 (283.15K) 0.02204 = 0.2204
mol molK mol
SPONTANEOUS at 10

kJ kJ kJ
at -10 C : G = 6.02 (263.15K) 0.02204 = 0.2204
mol molK mol
NONSPONTANEOUS at -10
2. 6CO2(g) +6H2 O(l) C6 H12 O6(s) +6O2(g)

Hf -393.5 -285.83 -1273.02 0 kJ/mol
S 213.6 69.91 212.1 205.0 J/molK
T = 298.15K
G = H T S
= [nHf , products nHf , reactants] T [nS , products nS , reactants]

kJ kJ kJ kJ
= (1) 1273.02 + (6) 0 (6) 393.5 + (6) 285.83
mol mol mol mol

J J J J
(288.15 K) (1) 212.1 + (6) 205.0 (6) 213.6 + (6) 69.91
molK molK molK molK

kJ
1000J
= 2880.17 kJ, N ON SP ON T AN EOU S
G = H - T S
+ Reaction is spontaneous at all T
Reaction is spontaneous at low T
+ + Reaction is spontaneous at high T
+ Reaction is nonspontaneous at all T
Grxn = nGf , products nGf , reactants
Gf, elements =0
Phase Changes (Constant T and P)
F ind q, w, U, H, S, and G f or 2mol H2 O

H2 O(l) H2 O(g)
Hvap = 40.67 kJ/mol

kJ
q = nHvap = (2 mol) 40.67 = 81.34 kJ
mol
w = (reversible, since slow process)
V2
= Pext dV = Pext (V2 V1 )
V1
= Pext (Vgas Vliq )

Assume Vgas >>> Vliq ; for liquid to solid reactions use density to convert
= P Vgas = nRT

J
= (2 mol) 8.314 (373.15 K) = 6205 J
molK
U = q + w
= 81.34 kJ 6.205 kJ = 75.135 kJ
H = qP = 81.34 kJ
kJ

nHvap (2 mol) 40.67 mol kJ
Svap = = = 0.218
Tb 373.15 K K

kJ
G = H T S = 81.34 kJ (373.15 K) 0.218 =0
K
Third Law of Thermodynamics
Spure, crystalline, solid at 0K =0
- you can calculate for the S and not only S
0K 298.15K
S = S298.15K S0K
S = S298.15K

q qP = nCP T qV = nCV T q = w 0

wirrev Pext dV 0 Pext dV Pext dV

V2
wrev P V = nRT 0 nRT ln Pgas dV
V1
U nCV T nCV T 0 w = nCV T
H nCP T nCP T 0 nCP T

T2 T2 V2
S nCP ln
T1
nCV ln
T1
nR ln
V1 0
Chemical Equilibrium
- the moment where there is no change in the concentration of reactants/products
- the reaction is still occurring (dynamic state)
Approaches to Equilibrium
Kinetic Approach
1
N2(g) + O2(g) N O2(g)
2

at equilibrium: Ratef orward = Ratebackward
1
Kf [N2 ] 2 [O2 ] = Kb [N O2 ]
Kf [N O2 ]
= 1
Kb [N2 ] 2 [O2 ]
Kf
= Keq /KC (equilibrium constant)
Kb
Thermodynamic Approach
- natural direction of reactions is toward equilibrium
- equilibrium: maximum entropy of the universe. lowest G of the system
- when G = 0, it has achieved the above conditions
1
N2(g) + O2(g) N O2(g)
2
G = G + RT ln Qa Q: reaction quotient
aN O 2 aN O 2
G = G + RT ln 1 Qa = 1
aN2 2 aO2 aN2 2 aO2
at equilibrium:
G = 0
0 = G + RT ln Ka
G = RT ln Ka
G
ln Ka =
RT
G
K a = e RT (thermodynamic/true equilibrium constant)
aN O2
Ka = 1
aN2 2 aO2
activity = true pressure = P

= activity coefficient (correction factor to account for non-ideal pressure
PN O2 N O2 PN O2
Ka = 1 = 1 1
(PN2 ) PO22 N2 O2
2 PN2 2 PO2
Ka = K KP
If gases are ideal, = 1, a = P

PN O 2 nRT
Ka KP = 1 P = = M RT = CRT
PN2 2 PO2 V
CRTN O2 CN O 2 1
KP = 1 = 1 (RT ) 2
CRTN2 CRTO2 2 CN2 CO22
ng
KP = KC (RT )
Example
kJ 1
Gf,N O2(g) = 51.84 T = 298.15K N2(g) + O2(g) N O2(g)
mol 2

Grxn = nGf,p nGf,r
kJ
= 51.84 1 mol (0 + 0) = 51.84 kJ
mol
G
K a = e RT
51.84 kJ

=e (8.314103 kJ/molK)(298.15 K)
= 8.27 1010
since the gases are ideal,

Ka = KP = 8.27 1010
KP = KC (RT )ng
KP 8.27 1010
KC = n
= 1
(RT ) g [(8.314 103 kJ/molK)(298.15 K)] 2
= 4.09 109
Manipulating Equations
1
N2(g) + O2(g) N O2(g) KP = 8.27 1010
2
1
2 N2(g) + O2(g) N O2(g) KP = (8.27 1010 )2
2

1 1 1
N2(g) + O2(g) N O2(g) KP = (8.27 1010 ) 2
2 2

1
1 N2(g) + O2(g) N O2(g) KP = (8.27 1010 )1
2
Adding/Subtracting
1
2 N2(g)
+ O2(g) O2(g) KC1
N O(g) 1 1
2 N2(g) + 2 O2(g) KC2
N O(g) + 12 O2(g) N O2(g) KC1 KC2
Quiz
2N O(g) N2(g) + O2(g) KP = 1 1030
3
3N O(g) + Br2(g) 3N OBr(g) KP = 715.5
2
1 1
[2N O(g) N2(g) + O2(g) ] (KP = 1 1030 ) 2
2
1 3 1
[3N O(g) + Br2(g) 3N OBr(g) ] (KP = 715.5) 3
3 2

1 1 1
Overall: N2(g) + O2(g) + Br2(g) N OBr(g) KP = 8.944 1015
2 2 2
G = RT ln Ka Ka KP
kJ
= (8.314 103 kJ/molK)(298.15 K)(ln 8.944 105 ) = 91.05
mol
Molecular Equilibrium
Solving Equilibrium Problems
1. Write the balanced equilibrium equation

2. ICE table
3. Relate equilibrium concentrations to K
4. Solve
Homogenous Equilibria
1. Given:
1 mol SO3(g) 2L vessel 303.15 K 12.5% decomposed at equilibrium
2SO3g 2SO2g O2g

I 0.5 M 2M 0M
C -0.0625 M +0.0625 M +(0.5)0.0625 M
E 0.4375 M 0.0625 M 0.03125 M
[SO2 ]2 [O2 ]
KC =
[SO3 ]2
(0.0625M )2 (0.03125M )
KC =
(0.4375M )2
KC = 6.38 104

ng 4 Latm
KP = KC (RT ) = 6.38 10 0.08206 (303.15 K)
molK
KP = 0.0159
2. Given:
PN O = 300 mmHg PCl = 250 mmHg Peq = 420 mmHg T = 473.15 K
NO(g) + O2(g) NOCl(g)

I 300 0M
C -x -(0.5)x +x
E 300-x 250-0.5x x
300 x + 250 0.5x + x = 420 x = 260

N O : 40mmHg Cl2 : 120mmHg N OCl : 260mmHg
PN OCl
KP = 1
PN O PCL
2
2
260/760
KP = 1
(140/760)(120/760) 2
KP = 16.36
KP 16.36
KC = n
= 1
(RT ) g Latm
0.08206 molK (473.15 K) 2
KC = 101.94
3. Given: Initial: 0.40 mol NH3 Equilibrium: 0.15 mol H2 at 2 atm
2NH3 N2 + 3H2
I (mol) 0.4 0 0
C (mol) -0.1 +0.05 +0.15
E (mol) 0.30 0.05 0.15
mT OT AL = 0.5 mol

PT = 2 atm
0.3 mol
P N H 3 = N H 3 PT = 2 atm = 1.2 atm
0.5mol 3
0.05 mol PN2 PH 2
(0.2)(0.6)3
PN2 = N 2 PT = 2 atm = 0.2 atm KP = 2 = = 0.030
0.5mol P N H3 (1.2)2
0.15 mol
PH2 = H 2 PT = 2 atm = 0.6 atm
0.5mol
QUIZ
Given: Initial: 0.112 mol O2 0.0400 mol N2 O in 2.00L Equilibrium: 0.0400 mol NO2
2N2 O(g) + 3O2(g) 4NO2(g)

I 0.02 M 0.56 M 0 [N O2 ]4 (0.02)4
KC = = = 23.21
C - 0.01 - 0.015 + 0.02 [N2 O]2 [O2 ]3 (0.01)2 (0.041)3
E 0.01 M 0.041 M 0.02 M
4. Given: Initial: 0.125 mol COCl2 in 2.00L KC = 8 at 298.15 K
COCl2(g) CO(g) + Cl2(g) [CO][Cl2 ] x2

I 0.125 M 0 0 KC = 8=
[COCl2 ] 0.125 x
C -x +x +x
E 0.125 - x M x x x = 0.123
At Equilibrium: [COCl2 ] = 0.002 M [CO] = 0.123 M [Cl2 ] = 0.123 M
Heterogenous Equilibria
N H4 Cl(s) N H3(g) + HCl(g)

aN H3 aHCl
Ka = aN H4 Cl = 1 (a = 1 for pure solids and liquids)
aN H4 Cl
= aN H3 aHCl = (P )N H3 (P )HCl
= N H3 HCl PN H3 PHCl
= K KP
KP (for ideal gases, = 1) = PN H3 PHCl
KC = [N H3 ][HCl]
[H2 ]
F e(s) + H2 O(l) F eO(s) + H2(g) KC = [H2 O]
2Ag(s) + 12 O2(g) Ag2 O(s) KP = PO
1
0.5
2
[CO]2
C(s) + CO2(g) 2CO(g) KC = [CO2 ]
1. Given: PT = 450 mmHg at 298.15 K
NH4 Cl(s) NH3(g) + HCl(g)

I - 0 0
C - +x +x
E - x x
PT = 450 mmHg = 2x
x = 225 mmHg
2
225
KP = PN H3 PHCl = = 0.0876
760
KP 0.0876
KC = n
= = 1.46 104
(RT ) g [(0.09206)(298.15)]2

2. Given: 2.5 mol NH4 HS in 2L KC = 1.2 104 at 303.15 K
NH4 HS(s) NH3(g) + H2 S(g)

KC = [N H3 ][H2 S]
I - 0 0
C - +y +y 1.2 104 = y 2
E - y y y = 0.011 M
At Equilibrium: [NH3 ]=0.011 M [H2 S]=0.011 M
3. Given: 0.30 mol CCl4 , 0.010 mol Cl2 in 2L KC = 0.0132 at 700 K
CCl4(g) C(s) + 2Cl2(g)

I 0.15 M - 0.005 M [Cl2 ]2 (0.005 + 2z)2
KC = 0.0132 =
C -z - + 2z [CCl4 ] 0.15 z
E 0.15 - z - 0.005 + 2z z = 0.0183
At Equilibrium: [CCl4 ] = 0.1317 M [Cl2 ] = 0.0416 M
Factors Affecting Equilibrium

Le Chatelier's Principle
- when a stress factor is applied to a system in equilibrium, the system will shift to relieve the
stress (relieve the balance)
factors: changes in concentration, P, V, T, addition of catalyst
2A(g) + B(g) P(g) + heat
1. Concentration
- changes in concentration of solids and pure liquids do not affect equilibrium
Addition of A: shift to the RIGHT Removal of A: shift to the LEFT

Addition of B: shift to the RIGHT Removal of B: shift to the LEFT
Addition of P: shift to the LEFT Removal of P: shift to the RIGHT
2. Pressure/Volume (for gases)

P (resulting in V) shift to the RIGHT P (resulting in V) shift to the LEFT
P, shift to the lesser number of moles) P, (shift to the higher number of moles)
addition of an inert gas at constant P: decreases the partial pressure

addition of an inert gas at constant V: no effect, additional pressure
3. Temperature
- alters the value of the rate constant
T: shift to the LEFT T shift to the RIGHT

T favors endothermic processes T favors exothermic processes
H>0 (heat in the reactants) H < 0 (heat in the products)
4. Catalyst
- no shift in equilibrium, they affect both the forward and backward reactions
Quantitative Approach
G = G + RT ln Q G = RT ln K Q < K, G < 0, forward shift

G = RT ln K + RT ln Q Q = K, G = 0, equilibrium
Q
G = RT ln Q > K, G > 0, backward shift
K

Example: Given: 0.5 M COCl2 in 2L KC = 8
COCl2(g) CO(g) + Cl2(g)

I 0.5 M 0 0 [CO][Cl2 ] a2
KC = 8=
C -a +a +a [COCl2 ] 0.5 a
E 0.5 - a a a a = 0.472
At Equilibrium: [COCl2 ] = 0.028 M [CO] = 0.472 M [Cl2 ] = 0.472 M

[CO][Cl2 ] (0.472)2
I 0.028 M 0.472 0.472 QC = = = 0.422
C + 0.5 [COCl2 ] 0.528
E 0.528 KC > Qc (forward shift)

[CO][Cl2 ] (0.472)(0.972)
I 0.028 M 0.472 0.472 QC = = = 16.39
[COCl2 ] 0.028
C + 0.5
E 0.972 KC < Qc (backward shift)
COCl2(g) CO(g) + Cl2(g) [CO][Cl2 ]

I 0.028 M 0.472 M 0.972 M KC =
[COCl2 ]
C +b -b -b
(0.472 b)(0.972 b)
E 0.028 + b 0.472 - b 0.972 - b 8=
0.028 + b
b = 0.0249
At New Equilibrium: [COCl2 ] = 0.0529 M [CO] = 0.4471 M [Cl2 ] = 0.9471 M
Temperature: alters K
G = RT ln Ka
G H T S
ln Ka = =
RT RT
H 1 S
ln Ka = + (vant Hoff equation)
R T R
1
Plot lnKa vs
T
slope: Endothermic: - Exothermic: +
S
y-int:
R
Two-point form:

Ka2 H 1 1
ln =
Ka1 R T2 T1
Ionic Equilibria
Nonelectrolyte - does not conduct electricity
- does not dissociate into ions
- molecular
Examples: organic molecules C6H12O6, C12H22O11, CO(NH)2
Electrolyte - solutions that conduct electricity (salts, acids, bases)
- dissociates into ions
Strong Electrolyte - strongly conducts electricity
- completely dissociates into ions
Examples: HCl (strong acid), NaOH (strong base), NaCl (salt)
Weak Electrolyte - partially dissociates into ions

Examples: CH3COOH (weak acid), NH3 (weak base), AgCl (partially soluble)
Theories on Acids and Bases
Arrhenius Acid: H+ producers Bases: OH- producers

+
HCl(aq) + H2 O(l) H3 O(aq) + Cl(aq)
N H3(aq) + H2 O(l) N H4(aq)
+
+ OH(aq)
+
HCl(aq) + N H3(aq) N H4(aq) + Cl(aq) (limitation)

- the substance must be in an aqueous solution
Bronsted-Lowry Acid: H+ donors Bases: H+ acceptors

+
HCl(aq) + H2 O(l) H3 O(aq) + Cl(aq)

acid 1 base 2 acid 2 base 1
N H3(aq) + H2 O(l) +
N H4(aq)
+ OH(aq)

base 1 acid 2 acid 1 base 2
+
HCl(aq) + N H3(aq) N H4(aq) + Cl(aq)

acid 1 base 2 acid 2 base 1
- water can be an acid or a base (amphoteric or amphiprotic)
- dependent on the partner of water
Lewis Acid: electron pair acceptors Bases: electron pair donors
- forms coordinate covalent bonds (only one atom donates the electron pair)
- not all Lewis acids are Bronsted-Lowry acids
- other species besides H+ can accept electron pairs
Example: central atoms in complexes
Examples of Lewis Acids: electron deficient (partially positive)

1. H+
2. metals
3. molecules with incomplete octets
Examples: BF3, AlCl3
4. CO2 / SO2 (with double bonds)
Lewis Base: electron rich (with lone pairs)
Acid Strength
- capacity to donate the proton (based from the Bronsted-Lowry theory)
1. Polarity of the H-X bond

- having the greatest proton-like characteristics (most positive)
2. Strength of the H-X bond
- must be connected trough a weaker bond to be donated more easily
3. Stability of Conjugate
- acids are stronger when their conjugate base is more stable
- unstable conjugate bases tend to reclaim the donated proton
Acid Strength for Binary Acids (HnX)

From LEFT TO RIGHT: Acidity INCREASES
Example: Acidity of CH4 < NH3 < H2O < HF
- due to the polarity of H-X bond / electronegativity
- HF has the most proton-like H+ (most positive)
From TOP TO BOTTOM: Acidity INCREASES

Example: Acidity of HF < HCl < HBr < HI
- bigger atomic size, longer bond length
- it becomes easier to donate the H+

Priority: the ability to donate (atomic size) over positivity of H+ (electronegativity)
From left to right, atomic size increases negligibly, so polarity is more prioritized.
Acid Strength of Oxyacids

More O atoms, HIGHER Acidity
Example: Acidity of HNO2 < HNO3
- Inductuve Effect: oxygen atoms exert a pull on the electron cloud, causing the H+ to be
more positive. O atoms, pull on electron cloud, positive H+
Stability of Conjugate Base

Assessment: looking at the negative charge
- the more atoms the electron is distributed to (by having more resonance structures), the
more spread the negativity is and therefore, the more stable the conjugate base is
HIGHER Electronegativity of Central Atom, HIGHER Acidity

- the H is not attached to the central atom. Therefore, the central atom only can pull the
electron cloud.
Stability of Conjugate Base

- so that the effect of the negative can be lessened, it may be pulled by the central atom, so
the higher the pull of the central atom, the more stable the conjugate base is.
Basicity
Acidity, Basicity
- the stronger the acid, the weaker is its conjugate base.
Examples:
Acidity: HF < HCl < HBr < HI Basicity: F- > Cl- > Br- > I-
Acidity: HNO3 > HNO2 Basicity: NO3- < NO2-
Acidity: NH3 < H2O < HF Basicity: N3- > O2- > F-
Ionization of Water
- water is amphoteric, so it can autoionize (Endothermic Reaction)
H2 O(l) + H2 O(l) H3 O(aq)

+
+ OH(aq)
KW = [H3 O+ ][OH ]
at 298.15 K, pure water, KW = 1.0 1014
[H3 O+ ] = 1.0 107 M [OH ] = 1.0 107 M
- the concentrations are so small that water is almost a nonelectrolyte
log KW = log[H3 O+ ] + log[OH ] at 298.15 K,

log[H3 O+ ] log[OH ] = log Kw Acid : [H3 O+ ] > 1.0 107 [OH ] < 1.0 107
pH + pOH = pKw pH < 7 pOH > 7
N eutral : [H3 O ] = [OH ] = 1.0 107
+
at 298.15 K, pH + pOH = 14
pH = pOH = 7
Base : [H3 O+ ] < 1.0 107 [OH ] > 1.0 107
pH > 7 pOH < 7
Strong Electrolytes
Strong Acids Strong Bases
HCl HBr HI NaOH KOH LiOH
HNO3 HClO4 HClO3 RbOH CsOH Ba(OH)2
H2SO4 (first ionization) Sr(OH)2

Levelling Effect:
Strongest acid that can exist in a solvent is the solvent's conjugate acid.
Strongest base that can exist in a solvent is the solvent's conjugate base.
- the degree of ionization is dependent on the solvent
Example: many acids that are weak in water fully ionize in liquid ammonia.
Weak Electrolytes
HA(aq) + H2 O(l) H3 O(aq)

+
+ A
(aq)
Ka - acid ionization/dissociation constant

[H3 O+ ][A ]
Ka = Examples: HF, organic acids (R-COOH)
[HA]
B(aq) + H2 O(l) BH(aq)

+
+ OH(aq)
Kb - base ionization/dissociation constant
[BH + ][OH ]
Kb = Examples: organic bases (R-NH2 )
[B]
Polyprotic Acids
H3 P O4(aq) + H2 O(l) H3 O(aq)

+
+ H2 P O4(aq) Ka1 = 7.5 103
H2 P O4(aq) + H2 O(l) H3 O(aq) + HP O4(aq)
+ 2
Ka2 = 6.2 108
2
HP O4(aq) + H2 O(l) H3 O(aq)
+ 3
+ P O4(aq) Ka3 = 4.2 1013
- the Ka becomes smaller after each ionization

- since the acid becomes more negative, removing the H+ becomes harder
ionization Ka
Salts
- product of the neutralization of an acid with a base
- the cation is from the base and the anion is from the acid
Example: NaCl Na from NaOH; Cl from HCl
Salts of Strong Acids and Strong Bases

+
KN O3(aq) K(aq) + N O3(aq)
from a strong base from a strong acid
no hydrolysis no hydrolysis
- both are conjugates of strong acids and bases so no hydrolysis occurs, pH 7
Salts of Weak Acids and Strong Bases

N aF(aq) N a+
(aq) + F(aq)
from a strong base from a weak acid
no hydrolysis
F(aq) + H2 O(l) HF(aq) + OH(aq)

(Kb )
pH > 7
Salts of Strong Acids and Weak Bases

+
N H4 Cl(aq) N H4(aq) + Cl(aq)
from a weak base from a strong acid
+
N H4(aq) + H2 O(l) H3 O(aq)
+
+ N H3(aq) (Ka ) no hydrolysis
pH < 7
More Examples:

KI(aq) + H2 O(l) KOH(aq) + HI(aq) neutral
N aN O3(aq) + H2 O(l) N aOH(aq) + HN O3(aq) neutral
N aN O2(aq) + H2 O(l) N aOH(aq) + HN O2(aq) basic
N H4 Br(aq) + H2 O(l) N H3(aq) + HBr(aq) acidic
N aCH3 COO(aq) + H2 O(l) N aOH(aq) + CH3 COOH(aq) basic
CH3 N H3 Cl(aq) + H2 O(l) CH3 N H2(aq) + HCl(aq) acidic
Relating Ka and Kb of conjugate acid-base pairs
(aq) + H2 O(l) HA(aq) + OH(aq)

A
[HA][OH ] [H3 O+ ]
Kb =
[A ] [H3 O+ ]
[HA]
Kb = [OH][H3 O+ ]
[A ][H3 O+ ]
1
Kb = KW
Ka
Ka Kb = Kw (for conjugate acid-base pairs)

- this also explains why when an acid is very strong, its conjugate base is weak
Salts of Weak Acids and Weak Bases
Example: NH4F
+
N H4(aq) F(aq)
from a weak base from a weak acid
+
N H4(aq) + H2 O(l) H3 O(aq)
+
+ N H3(aq) (Ka )
F(aq) + H2 O(l) HF(aq) + OH(aq)

(Kb )
Ka > Kb acidic salt

Ka = Kb neutral salt
Ka < Kb basic salt
Kb : N H3 = 1.8 105 Ka : HF = 6.8 104

Ka : N H4+ = 5.56 1010 > Kb : F = 1.47 1011
acidic salt
Amphoteric Compounds
H2 CO3(aq) + H2 O(l) H3 O(aq)

+
+ HCO3(aq) Ka1

HCO3(aq) + H2 O(l) H3 O(aq)
+ 2
+ CO3(aq) Ka2

N aHCO3 N a+
(aq) + HCO3(aq) HCO3 is amphoteric

HCO3(aq) + H2 O(l) H3 O(aq)
+ 2
+ CO3(aq) Ka2 = 5.6 1011

HCO3(aq) + H2 O(l) H2 CO3(aq) + OH(aq)
KW
Kb = K a1
= 2.33 108
Kb is larger, so HCO3 is more basic than acidic
From H3 P O4(aq) + H2 O(l) H3 O(aq)

+
+ H2 P O4(aq) Ka1 = 7.5 103

H2 P O4(aq) + H2 O(l) H3 O(aq)
+ 2
+ HP O4(aq) Ka2 = 6.2 108
HP O4(aq) + H2 O(l) H3 O(aq) + P O4(aq)
2 + 3
Ka3 = 4.2 1013
Find out if Na3PO4, Na2HPO4 and NaH2PO4 are basic or acidic.
Common Ion Effect

- the common ion suppresses the ionization of weak electrolytes.
% ionization pH
0.10 M HCl 100% 1.0
0.10 M HCl + 0.05 M NaCl 100% 1.0
0.10 M HOAc 1.34% 2.87
0.10 M HOAc + 0.05 M NaOAc 0.036% 4.44
Weak Bases lower ionization lower pH
Buffer Solutions
- solutions that resist drastic changes in pH upon addition of small amount of acid or base
- because buffers have acids and bases that can neutralize that addition
- biological samples are very sensitive to pH so they need to have buffers
- buffers have ranges in pH that they are effective at (1.0 pH)
- composed of a weak acid/base and its conjugate
HA(aq) + H2 O(l) H3 O(aq)

+
+ A
(aq)
[H3 O+ ][A ]
Ka =
[HA]
[A ]
log Ka = log[H3 O+ ] + log
[HA]
[A ]
log[H3 O+ ] = log Ka + log
[HA]
[A ]
pH = pKa + log (Henderson-Hasselbalch Equation)
[HA]
[BH + ]
pOH = pKb + log
[B]

- the closer pH to the pKa, the better the buffer

- pH = pKa 1.0 (buffer capacity)
Initial pH + 10mL 1M HCl + 10 mL 1M NaOH

Buffer 7.00 6.98 7.02
H2O 7.00 1.71 12.29
- you can form a buffer by neutralizing the acid alone, thus forming a conjugate base (like in
titration)
Acid-Base Indicators
- weak organic acids and weak organic bases that are sensitive to pH changes
HIn(aq) + H2 O(l) H3 O(aq)

+
+ In
(aq)
The acid formed has a different color than the base formed.
pH range
[In ]
[HIn] 10 base color predominates +1
pKa
[HIn]
10 acid color predominates -1
[In ]
- pH ranges are dependent on pKa

Examples: phenolphthalein, bromthymol blue

Acid-Base Titration
- technique used to determine the concentration of an acid or base, using a known concen-
tration of a known base or acid
titrant: known base or acid

analyte: unknown acid or base
indicator: 2 to 3 drops are added
- a small amount because indicators are also acids/bases and can affect titration
Complex Ion Equilibrium

- involves the formation of a complex
(aq) + 4N H3(aq) Cu(N H3 )4(aq)

Cu2+ + 2N H3(aq) Ag(N H3 )+
2+ +
Ag(aq) 2(aq)
Kf : formation constant Kf : formation constant

[Cu(N H3 )2+
4 ] [Ag(N H3 )2+
2 ]
Kf = = 5 1013 Kf = = 1.7 107
[Cu ][N H3 ]4
2+
[Ag ][N H3 ]2
+
- since formation constants are very large, complex ion formation is very favorable
Slightly Soluble Salts

P bI2(s) P b2+
(aq) + 2I(aq) Al(OH)3(s) Al(aq)
3+
+ 3OH(aq)
KSP = [P b2+ ][I ]2 = 1.4 108 KSP = [Al3+ ][OH ]3 = 1.8 1033
Ksp = solubility product constant
- solubility product constants are very small, therefore, the salts are very sparingly soluble
- you cannot say which is more soluble by looking at the Ksp unless they have the same
formula type
Factors Affecting Solubility

1. Temperature
- temperature alters Ksp but it rarely affects the solubility of slightly soluble salts
- since Ksp are small, the change temperature makes is not large enough
- there are exceptions like PbCl2 (Ksp = 1.7 x 10-5)
Example: PbCl2 dissolves in hot water while AgCl doesnt (Ksp = 1.8 x 10-10)
2. Common Ion Effect

- the presence of the common ion suppresses the dissolution of salts
3. Uncommon Ion Effect

AgBr(s) Ag(aq)
+
+ Br(aq) in 0.10 M KN O3
- the ion products form ion pairs with the uncommon ions (Ag+ with NO3- and Br- with K+)
- the amount of free ions decrease, so the equilibrium will shift forward (solubility)
4. Presence of Complexing Agent

- increases solubility since complex ion formation reduces the amount of an ion formed
- equilibrium shifts forward
5. pH
- only affects salts with basic anions (conjugate bases of weak acids)
- larger amount of basic anions (higher pH) shifts equilibrium backwards
- precipitate forms
- larger amount of acidic anions, (lower pH) neutralizes basic anions
- equilibrium shifts forward, precipitate dissolves

M g(OH)2(s) M g(aq)
2+
+ 2OH(aq) P bF2(s) P b2+
(aq) + 2F(aq)

OH(aq) +
+ H3 O(aq) 2H2 O(l)
F(aq) +
+ H3 O(aq) HF(aq) + H2 O(l)

Exceptions:
CuS CdS PbS NiS FeS ZnS
Ksp 6 1037 8 1028 3 1028 3 1020 6 1019 2 1025
- for CuS, CdS and PbS, an increase in pH doesn't increase their solubility
-since their Ksp are low, the removal of the basic anion doesn't cause a large shift forward
Precipitation
P bI2(s) P b2+
(aq) + 2I(aq)
Ksp = [P b2+ ][I ]2

Qsp = [P b2+ ]0 [I ]20 Q: ion product
Q < Ksp no precipitate (unsaturated solution)

Q = Ksp maximum amount dissolved (saturated solution)
Q > Ksp precipitate forms
Fractional Precipitation
- precipitation of different compounds in a specific order
- you cannot compare by looking at the Ksp unless they have the same formula type and
concentration.
- if the above is true, then the compound with the lowest Ksp forms first
Dissolution
1. Variation in Temperature
- no significant effect on most salts because of their low Ksp
2. Variation in pH
- only applicable to salts with basic anions
BaCO3(s) Ba2+ 2
(aq) + CO3(aq)
2
CO3(aq) +
+ H3 O(aq) HCO3(aq)

+ H2 O(l)
(aq) + H3 O(aq) H2 CO3(aq) +H2 O(l)

HCO3 +

CO2 +H2 O
3. Presence of Complexing Agent

4. Presence of Oxidizing Agent
3CuS(s) + 8HN O3(aq) 3Cu(N O3 )2(aq) + 2N O(g) + 3S(s) + 4H2 O(l)
Amphoteric Hydroxides
- soluble on both acids and bases
+
Al(OH)3(s) + 3H3 O(aq) Al(aq)
3+
+ 6H2 O(l)

Al(OH)3(s) + OH(aq) Al(OH)
4(aq)
+
Zn(OH)2(s) + 3H3 O(aq) Zn2+
(aq) + 4H2 O(l)

Zn(OH)2(s) + 2OH(aq) Zn(OH)2
4(aq)
Electrochemistry
- deals with interconversion of electrical energy and chemical energy
- deals with reduction-oxidation reactions

Electrochemical Cell
- cells that harness electrical energy from chemical energy in solution
Example: Daniell Cell
electrode - metal where the reduction/oxidation reaction occurs

anode: (- electrode) oxidation (AN OX)
cathode: (+ electrode) reduction (RED CAT)
electron flow: from anode to cathode
salt bridge - saturated salt solution, usually KCl or KNO3

- cation and anion have equal mobilities
anode: Zn2+ is formed, excess of positive charge, anion is attracted
cathode: SO42- is formed, excess of negative charge, cation is attracted
- retains neutrality of solution
Two Types of Electrochemical Cell

1. Galvanic or Voltaic Cell: generates electricity
- chemical energy to electrical energy
- reaction is spontaneous
- work is done by the system
- anode: (-) electrode cathode: (+) electrode
2. Electrolytic Cell: consumes electricity
- electrical energy to chemical energy
- reaction is nonspontaneous, electricity is needed to drive it
- work is done by the surroundings
- anode: (+) electrode cathode: (-) electrode
Cell Potential / Cell EMF

- sum of the contribution of both half cell potentials
Electrode potential
- cannot be exactly determined
- measured using a reference electrode
- Standard Hydrogen Electrode (SHE)
+
2H(aq) + 2e H2(g) E = 0V
- electrode potential arbitrarily assigned as 0
- used platinum (an inert electrode, doesnt react) as the solid electrode
-covered with platinum to increase surface area for more adsorption of H+
- alternative inert electrode: C(s, graphite)
- paired up different electrodes with the SHE to determine their respective potentials
- convention: E must be written as the REDUCTION potential
- oxidation potential = -E
E, chance to be reduced, strength as Oxidizing Agent

Example: Cu2+ vs Zn2+ Cu2+ is reduced, Cu2+ is a stronger Oxidizing Agent
E, chance to be oxidized, strength as Reducing Agent
Example:
Arrange the following in order of:
1. Increasing strength as Oxidizing Agent: Cl2, Br2, Ce4+ Br2 < Cl2 < Ce4+
2. Increasing strength as Reducing Agent: Ni, Mn, Cd Ni < Cd < Mn
3. Decreasing strength as Oxidizing Agent in acidic medium:
Cr2O72-, MnO4-, H2O2 H2O2 > MnO4- > Cr2O72-
4. Decreasing strength as Reducing Agent: Co, Ag, Fe Fe > Co > Ag
Cell Representation: Anode | Anode solution || Cathode solution | Cathode

Example: Zn | Zn2+ || Cu2+ | Cu
Example:
Calculate the standard cell potential of the following:
1. Zn|Zn2+ ||N i2+ |N i

Anode: [Zn2+ + 2e Zn(s) ] E = 0.76V
Cathode: N i2+ + 2e N i(s) E = 0.25V

Cell Reaction: Zn(s) + N i2+ N i(s) + Zn2+ Ecell = Ecathode Eanode

Ecell = 0.51V

Ecell > 0, Galvanic
If Ecell > 0, you may say that the reaction is spontaneous at standard state
- the cell is GALVANIC
If Ecell < 0, you may say that the reaction is nonspontaneous at standard state
- the cell is ELECTROLYTIC
2. Ag|Ag + ||F e2+ |F e

Anode: 2[Ag + + e Ag(s) ] E = 0.80V
Cathode: F e2+ + 2e F e(s) E = 0.44V

Cell Reaction: 2Ag(s) + F e2+ F e(s) + 2Ag + Ecell = 1.24V

Ecell < 0, Electrolytic
Note: Changing the moles of the reaction doesn't change E, it its intrinsic.
To drive the reaction in number 2, you must apply more than 1.24V electricity
3. Cr|Cr3+ ||Cl , Cl2(g) |P t

Anode: 2[Cr3+ + 3e Cr(s) ] E = 0.74V
Cathode: 3[Cl2(g) + 2e 2Cl ] E = 1.36V
3+
Cell Reaction: 3Cl2(g) + 2Cr(s) 6Cl(aq) + 2Craq Ecell = 2.10V

Ecell > 0, Galvanic
Thermodynamics of Electrochemical Cells

n: moles of electrons (Faraday)
G = Welectrical
F: Faradays Constant: 96,485 C/mol e-
G = nF E
E: electrode potential

E > 0, G < 0, spontaneous, GALVANIC
E = 0, G = 0, equilibrium, neither
E < 0, G > 0, nonspontaneous, ELECTROLYTIC
G = G + RT ln Q
nF E = nF E + RT ln Q
RT
E = E ln Q Nernst Equation
nF
J
8.314 molK 298.15 K
at 25 C, E = E C
2.303 log Q
n 96485 mol
0.0592
E = E log Q (at 25 C)
n
Determine the potential of the following cells:

1. P b|P b2+ (0.010M )||Co3+ (0.050M ), Co2+ (0.0040M )|P t
Anode: [P b2+ + 2e P b(s)] E = 0.13V
Cathode: 2[Co3+ + e Co2+ ] E = 1.82V

Cell Reaction: P b(s) + 2Co3+ P b2+ + 2Co2+ Ecell = 1.95V
0.0592 [P b2+ ][Co2+ ]2

Ecell = Ecell log
n [Co3+ ]2
0.0592 (0.010)(0.0040)2
Ecell = 1.95V log = 2.07V
2 (0.050)2
2. Cu|Cu2+ (0.50M )||Cr2 O72 (0.060M ), H + (0.0040M ), Cr3+ (0.080M )|P t

Anode: 3[Cu2+ + 2e Cu(s)] E = 0.34V
Cathode: Cr2 O72
+ 14H + + 6e 2Cr3+ + 7H2 O E = 1.33V
Cell Reaction: 3Cu(s) + Cr2 O72 + 14H + 3Cu2+ + 2Cr3+ + 7H2 O
Ecell = 0.99V
0.0592 [Cu2+ ]3 [Cr3+ ]2

Ecell = Ecell log
n [Cr2 O72 ][H + ]14
0.0592 (0.50)3 (0.080)2
Ecell = 0.99V log = 0.677V
6 (0.060)(0.0040)14
Applications
1. Determination of Equilibrium Constant
G = RT ln K
nF E = RT ln K
nF E
ln K =
RT
nF E nE
K=e RT K = 10 0.0592 at 25 C
Example:
1. P b(s) + 2CO3+ P b2+ + 2Co2+ Find K

Ecell = Ecathode Eanode = 1.82V (0.13V ) = 1.95V
nE 21.95V
K = 10 0.0592 = 10 0.0592 = 7.56 1065

2. M g(s) + 2HCl(aq) M gCl2(aq) + H2(g) Find K
Anode: [M g 2+ + 2e M g(s)] E = 2.37V
Cathode: 2H + + 2e H2(g) E = 0V

Cell Reaction: M g(s) + 2H + M g 2+ + H2(g) Ecell = 2.37V
nE 22.37V
K = 10 0.0592 = 10 0.0592 = 1.17 1080
since K is very very large, the reaction is complete
2. Calculation of Other Equilibrium Constants
1. Ag|Ag + ||Cl , AgCl|Ag

AgCl(s) Ag(aq)
+
+ Cl(aq)
Anode: [Ag + + e Ag(s)] E = 0.80V

Cathode: AgCl(s) + e Ag(s) + Cl(aq) E = 0.22V
Cell Reaction: AgCl(s) Ag(aq) + Cl(aq)
+
Ecell = 0.58V
nE 10.58V
Ksp = 10 0.0592 = 10 0.0592 = 1.59 1010
Quiz
P t|F e3+ (1.20M ), F e2+ (0.0075M )||M nO4 (0.0020M ), H + , M n2+ (2.50M )|P t
Anode: 5[F e3+ + e F e2+ ] E = 0.77V

Cathode: M nO4 + 8H + 5e M n2 + 4H2 O] E = 1.51V

Cell Reaction: M nO4 + 8H + + 5F e2+ M n2 + 4H2 O + 5F e3+ Ecell = 0.74V
0.0592 [M n2+ ][F e3+ ]5

Ecell = Ecell log >0
n [M nO4 ][H + ]8 [F e2+ ]5
0.0592 (2.50)(1.20)5
0.74V log >0
5 (0.0020)[H + ]8 (0.0075)5

0.0592 1.31072 1014 5
log > 0.74
5 [H + ]8 0.0592
1.31072 1014
log < 62.5
[H + ]8
1.31072 1014
log < [H + ]8
3.162 1062
[H + ] > 8.96 107 M
pH < 6.05
Concentration Cell
electrode: determines concentration or activity
reference electrode: potential does not vary with the concentration of the analyte
- independent, fixed potential
Example: SCE - standard calomel electrode (Hg2Cl2)
indicator electrode: sensitive to concentrations of analyte
- potential varies with concentration of analyte
pH meter: reference electrodes: SCE, Ag|Ag+
indicator electrode:
- glass tipped with solution of known pH
- E is generated from difference in potentials between electrode and
surroundings
- calibration: using buffers, constant pH of 4/7/10
- setting what concentration will be pH 4/7/10
- checking the proper slope
- in order to find the relationship of potential and pH

For SHE: Ecell = 0.0592pH
Electrolytic Cells
Types of electrical Conduction
1. Electronic Conduction (Metallic Conduction)
- the metal is the conductor because of a large sea of electrons
2, Electrolytic Conduction
- electrolytes are conductors - presence of ions
Electrolysis - application of electricity to a solution of electrolyte to drive a reaction
Mechanism of Electrolysis
1. Migration of Ions towards the electrodes
- Cations to Cathode - Anions to Anode
2. Reaction occurs at the electrodes
- Cathode: Reduction - Anode: Oxidation
Factors that affect electrode reaction

1. Nature of Electrode
a. Active: May also oxidize if it is the anode electrode
b. Inert: No reaction (Pt, Cgraphite)
2. Nature of Electrolyte
a. Molten: Pure liquid, contains only the cation and anion
b. Aqueous: In water solvent, involves competition with water
Predict the products formed:

1. Electrolysis of molten LiBr between Pt electrodes
Electrode: Inert Electrolyte: Molten
Product
Anode: 2Br Br2 + 2e E = 1.07V liquid/gaseous Br2
Cathode: Li+ + e Li(s) E = 3.05V deposit of Li(s)

2. Electrolysis of aqueous LiBr in Pt electrodes
Electrode: Inert Electrolyte: Aqueous
Cathode: Li+ + e Li(s) E = 3.05V

2H2 O + 2e H2(g) + 2OH(aq) E = 0.83V
Anode: 2Br Br2 + 2e E = 1.07V

2H2 O O2(g) + 4H + + 4e E = 1.23V
3. Electrolysis of molten NaCl between Pt electrodes

Electrode: Inert Electrolyte: Molten
Cathode: N a+ + e N a(s)
Anode: 2Cl Cl2(g) + 2e

4. Electrolysis of aqueous NaCl between Pt electrodes

Cathode: N a+ + e N a(s) E = 2.71V

2H2 O + 2e H2(g) + 2OH(aq) E = 0.83V
Anode: 2Cl Cl2 + 2e E = 1.36V

2H2 O O2(g) + 4H + + 4e E = 1.23V
Useful products: H2(g) , Cl2(g) , N aOH
EXCEPTION FOR Cl- vs H2O

overpotential - when gases are involved, an overpotential happens
- added potential
- added for O2 is more than added for Cl2
- Efinal O2 > Efinal Cl2
- dependent on nature of gas
- only applies between Cl- and H2O
5. Electrolysis of Aqueous AgNO3 with Ag electrodes

Electrode: Active Electrolyte: Aqueous
Cathode: Ag + + e Ag(s) E = 0.80V

2H2 O + 2e H2(g) + 2OH(aq) E = 0.83V

Anode: XN O3 most oxidized form of N
2H2 O O2(g) + 4H + + 4e E = 1.23V
+
Ag(s) Ag + e E = 0.80V
if Oxidation State = Valence electrons, it is the most oxidized form
Faraday's Law of Electrolysis

- products formed n current
Q: charge (coulomb)
Q = It I: current (ampere, C/s)
t: time
Q n: moles of electrons (Faraday)

n e =
F F: Faradays constant (96485 or 96500 C/mol e-)
Example: electrolysis of molten CaCl2 between Pt electrodes using 10A current for 5 min

Cathode: Ca2+ + 2e Ca(s)

Anode: 2Cl Cl2(g) + 2e

10 C 1 mol e 1 mol Ca 40.08 g Ca
WCa = 300 s = 0.623 g
s 96500 C 2 mol e 1 mol Ca

10 C 1 mol e 1 mol Cl2 22.4 L Cl2
VCl2 , ST P = 300 s = 0.348 L = 348 mL
s 96500 C 2 mol e 1 mol Cl2
Given: Coin, 2.5 cm diameter, 0.15 cm height, 0.0025 cm layer of Au

= 19.3 g/cc, I =0.100 A, 90% yield
Find mass of Au and the time needed to form the Au layer
VAu = V = (r2 h)f (r2 h)i

VAu = [(1.2525)2 (0.155) (1.25)2 (0.15)]
VAu = 0.0276 cc
VAu = SA thickness
SA = 2 r2 + dh
SA = 2 (1.25 cm)2 + (2.5 cm)(0.155 cm) = 11.03 cm2
VAu = 11.03 cm2 0.0025 cm = 0.0276 cc

19.3 g
WAu = 0.0276 cc = 0.533 g
cc
Au(CN )
4 + 3e Au(s) + 4CN

10
1 mol 3 mol e 96485 C s
0.533 g = 8703 s = 145.05 min
196.97 g 1 mol mol e 0.100 C 9
Coordination Chemistry
- study of coordination compounds
History
- started with CoCl36NH3, fascinated scientists
- Alfred Werner
Compounds have Two Valences

1. Principal/Primary Valence - oxidation number
2. Secondary/Subsidary Valence - coordination number
(number of coordinate covalent bonds)
- changed CoCl36NH3 to [Co(NH3)6]Cl3

Primary Valence: +3 Secondary Valence: 6
Complex / Coordination Compound

- central metal atom - attached ligands
- formed by a Lewis acid-base reaction
H3N: Ag+ :NH3 Lewis Acid: Ag+ Lewis Base: NH3

Donor Atom: N (forms the coordinate covalent bond)
Coordination Number: number of donor atoms that surround the central atom
First Coordination Sphere: composed of the central atom and its attached ligands
Example: [Ag(NH3)2]+
K4[Fe(CN)6](aq) 4K+(aq) + Fe(CN)64-(aq) (first coordination sphere stays intact)
Conductivity

- electrical conductivity depends on the number of ions that dissociate
Platinum(IV) Complex Molar Conductance (0.001 M)

[Pt(NH3)6]Cl4 523
[PtCl2(NH3)4]Cl2 228
[PtCl4(NH3)2] 0
Note: Only Complexes with Coordination Numbers 2, 4 and 6 will be studied for Chem 18
Shapes of Complexes
Coordination Number Shape
2 Linear
4 Tetrahedral or Square Planar
6 Octahedral
Example: [PtCl5(NH3)] coordination number: 6 shape: octahedral
Ligands
- denticity: number of donor atoms available
monodentate: one donor atom
Examples: H2O, NH3, Cl-, Br-, I-, F-, CN-, CO (C donates), SCN- OH-
bidentate: 2 donor atoms

- glycinate
polydentate: EDTA: 6 donors: 4 O, 2 N
- polydentate ligands are good chelating agents

Biological Complexes:
hemoglobin: central atom: Fe ligands: heme, globin, oxygen
Complex Primary Valence Secondary Valence Denticity

[Ru(NH3)5(H2O)]Cl2 +2 6 ALL monodentate
Br-: monodentate
[CoBr2(en)2]2SO4 +3 6
en: bidentate
[Fe(CO)5] 0 5 ALL monodentate
C2O42-: bidentate
Mg[Cr(C2O4)2(H2O)2]2 +3 6
H2O: monodentate
Nomenclature of Complexes
1. Cation is named first before the anion
2. In complex parts, ligands are named first before the metal
a. alphabetical order (not including greek prefixes)
b. Greek prefixes to specify number of a ligand
- di, tri, tetra, penta, etc.
- if the ligand already contains a greek prefix, use bis, tris, tetrakis, pentakis and
enclose the ligand it describes in a parenthesis
Ag(NH3)2+ diamminesilver(I)
[Fe(en)3]3+ tris(ethylenediamine)iron(III)
- if adding a Greek prefix can mean another thing for the ligand, use bis, tris etc.
(CH3NH2)2 bis(methylamine) dimethylamine: (CH3)2NH2
(C2O42-) bis(oxalato) bioxalate: HC2O4-
c. ligands that end with ide o bromide - bromo, cyanide - cyano, chloride - chloro
d. ligands that end with ite ito end with ate ato
carbonate - carbonato ONO- - nitrito
C2O42- - oxalato sulfate - sulfato
nitrate - nitrato
e. neutral ligands: same name
3. If the complex is an anion (has a negative charge), end with the latin name (if any) + -ate
K4[Fe(CN)6] potassium hexacyanoferrate(II)
If the complex is neutral or a cation, end it with the metal's english name
[PtCl(NH3)5]Cl3 pentaamminechloroplatinum(IV) chloride
[Fe(en)3](NO3)3 tris(ethylenediamine)iron(III) nitrate
4. Add the oxidation number in parenthesis after the name of the metal
Formula Writing
1. Write the cation first before the anion
2. For Complexes
a. the metal is written first before the ligands
b. anionic ligands are written first before neutral
c. if many ligands, list in alphabetical order based on the first letter of the symbol,
following first the rules above
Example:
1. tetracarbonylnickel(0) [Ni(CO)4]
2. tetraamminedichlorocobalt(III) chloride [CoCl2(NH3)4]Cl
3. potassium hexacyanoferrate(III) K3[Fe(CN)6]
4. dichlorobis(ethylenediamine)platinum(IV) nitrate [PtCl2(en)2](NO3)2
5. tetraamminechromium(II) hexafluoroferrate(III) [Cr(NH3)4]3[FeF6]2
Name the following:

1. [Fe(OH)(H2O)5]Br2 pentaaquahydroxoiron(III) bromide
2. Ca[Au(CN)4]2 calcium tetracyanoaurate(III)
3. [Zn(en)2][PtCl(CO3)O(H2O)2]2
bis(ethylenediamine)zinc(II) diaquacarbonatochlorooxoplatinate(IV)

4. [Cr(SO4)(NH3)5][Co(C2O4)2(NH3)2]
pentaamminesulfatochromium(III) diamminebis(oxalato)cobaltate(III)
5. [Co(NO2)(SCN)(CO)3(NH3)][RuCl2I3(H2O)]
amminetricarbonylnitrothiocyanatocobalt(III) aquadichlorotriiodoruthenate(III)
Give the formula of the following:

1. triammineaquadihydroxochromium(III) nitrate [Cr(OH)2(H2O)(NH3)3]NO3
2. potassium diaquatetrabromovanadate(III) K[VBr4(H2O)2]
3. tetraamminecarbonatocobalt(III) tetrahydroxoaluminate(III) [Co(CO)(NH3)4][Al(OH)4]
4. dicarbonylethylenediamineplatinum(II) tetraiodomercurate(II) [Pt(CO)2(en)][HgI4]
5. diaquabromotriphosphinemanganese(III) chlorohydroxobis(oxalato)rhodate(III)
[MnBr(H2O)2(PH3)3]3[RhCl(C2O4)2(OH)]2
Isomerism
Isomer: compounds with the same formula but different arrangement of atoms
Structural: different links and bonds
Stereoisomerism: different spatial arrangements
Structural Isomers
1. Ionization Isomers: differs by the exchange of a ligand with an atom or neutral molecule
outside the coordination sphere

[Co(SO4)(NH3)5]Br [CoBr(NH3)5]SO4
Red Color Violet
AgBr(s) + AgNO3 no precipitate
no precipitate + BaCl2 BaSO4(s)
2. Hydrate Isomers: differ by an exchange of water between a molecule of water and a

ligand in the coordination sphere
Complex Color + AgNO3

[Cr(H2O)6]Cl3 violet 3 AgCl(s)
[CrCl(H2O)5]Cl2H2O green 2 AgCl(s)
[CrCl2(H2O)4]Cl2H2O green 1 AgCl(s)
3. Linkage Isomers: ligands are linked through different atoms

Examples: -NO2 nitro -SCN- thiocyanato
-ONO nitrito -NCS- isothiocyanato
-CN- and -NC- cyano

4. Coordination Isomers: exchange of ligands between coordination centers
Examples: [Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4]
[Pt(NH3)4][PtCl4] and [PtCl2(NH3)4][PtCl4]
Optical Isomers (Enantiomers)

- nonsuperimposable mirror images
- must be chiral (asymmetrical)
- must not be achiral (symmetrical)
- achieved through bidentate ligands
- they are optically active - they can rotate plane-polarized-light
- mirror images rotate the light in opposite directions
Polarimeter - measures optical activity

- creates plane polarized light and shows how a solution of
enantiomers rotate it

Direction of Rotation
dextorotatory - clockwise turn (to the right)
levorotatory - counterclockwise turn (to the left)
- if a certain complex is dextorotatory, its mirror image is levorotatory and vice versa
Diastereomers - nonsuperimposable, nonmirror images with each other
Theories on Bonding
Valence Bonding Theory (Localized Electron Model)
- coordinate covalent bond: overlap of 1 empty orbital and 1 filled orbital
- describes bonding using hybrid orbitals and electron pairs
- overlap of empty metal orbital and filled ligand orbital
Octahedral
1. CoF63- 27
Co: [Ar]4s23d7
Co3+: [Ar]3d6
Co3+ : _ _ _ _ __ __ __ __ __ __ __ __ __
3d 4s 4p 4d
_ _ _ _ __ __ __ +6 e- pairs from ligands

3d 4s 4p 4d
_ _ _ _ hybridization to sp3d2
3d sp3d2

OUTER ORBITAL COMPLEX
2. Co(CN)63- 27
Co: [Ar]4s23d7
Co3+: [Ar]3d6

Co3+ : _ _ _ _ __ __ __ __ __ __ ELECTRON PAIRING
3d 3d 4s 4p
+6 e- pairs from ligands

3d 4s 4p
hybridization to d2sp3
3d d2sp3
INNER ORBITAL COMPLEX
- if 3d orbitals are used for coordinate covalent bonds, stronger metal-ligand bonds are
formed, energy is needed to pair the electrons of the d orbitals
energy released during bond formation > pairing energy

- enough energy is obtained from bond formation to pair the electrons of the 3d orbitals
energy released during bond formation < pairing energy

Tetrahedral
CoCl42- Co2+: [Ar]3d7
Co2+ : _ _ _ __ __ __ __ __ __ __ __ __
3d 4s 4p 4d

_ _ _ +4 e- pairs from ligands
3d 4s 4p
_ _ _ hybridization to sp3
3d sp3

Square Planar
Ni(CN)42- Ni2+: [Ar]3d8

Ni2+ : _ _ __ __ __ __ __ ELECTRON PAIRING
3d 3d 4s 4p
__ +4 e- pairs from ligands

3d 4s 4p
hybridization to dsp2
3d dsp2
Crystal Field Theory

- explains bonding in terms of electrostatic forces
Types of Interaction
1. Electrostatic attraction between metal ion and ligand
2. Electrostatic repulsion between lone pairs on the ligands and the electrons in the d orbit-
als of the metal
Octahedral
- the orbitals dx^2-y^2 and dz^2 are hit by ligands directly when they approach so they must be
as electron-free as possible
- also, the direct hit causes these two orbitals to have higher energy, so a split occurs
Higher orbitals: x2-y2 and z2 are the eg Lower orbitals xy, yz and xz are the t2g
: crystal field splitting energy
Color
- color is shown because it reflects the color or it absorbs the compliment color

Red: wavelength, Violet: wavelength,
- when a complex absorbs light, its electrons become excited and there is an increase in
energy which is equal to the crystal field splitting energy (). It absorbs an amount of energy
to do so, therefore, you can determine the color absorbed and reflected (its compliment).
hc
= hv =

- The example on the left absorbs blue-green light

with a wavelength of 495 nm, this absorbed energy
excites the electron and promotes it to the eg orbital
- the size of crystal field splitting is dependent on the nature of the ligands
- interaction, , wavelength absorbed, splitting
Spectrochemical Series
- list of ligands in order of their abilities to split d orbitals
I < Br < Cl < OH < F < H2 O < CN S < N H3 < en < N O2 < CN < CO

Weak-field ligands Strong-field ligands
- strong field ligands usually contain N (except for CO)
Examples:
CoF63- (green) Co(CN)63- (yellow)
(too-high for electrons to reach)
eg
_ _
eg
_ _
t2g t2g
PARAMAGNETIC (high spin) DIAMAGNETIC (low spin)
- the crystal field theory accounts for the magnetic properties and color of complexes
Square Planar Tetrahedral
__
x2-y2 (directly hit)
__ __ __ (t2g)
__
xy (lobes near ligands)
__ __ __ (eg)
z2 (collar interaction)
__ __
xz yz

Example:
Ni(CN)2- Ni2+:[Ar]3d8 CoCl42- Co2+:[Ar]3d8
__ (too high to reach)

_ _ _ (t2g)

(eg)
- for square planar and tetrahedral complexes, the spin is related to the geometry
Square Planar: High Spin Tetrahedral: Low Spin
Geometry of Complexes of Metals

Linear: Ag+, Au+, Cu+
Square Planar: Cu2+, Ni2+, Pd2+, Pt2+
Tetrahedral: Al3+, Au+, Cd2+, Zn2+, Co2+, Ni2+
Octahedral: Co2+, Co3+, Cr3+, Cu2+, Fe2+, Fe3+, Pt4+, Ni2+
Ni2+: Strong-Field Ligand: Square Planar Weak Field Ligand: Tetrahedral
Examples:
1. [Cr(en)3]3+ Cr3+: [Ar]3d3 2. [Mn(CN)6]3- Mn3+:[Ar]3d4

eg eg
_ _ _ _ _

t2g
t2g
3.[Co(H2O)6]2+ Co2+:[Ar]3d7 4. [FeCl4]- Fe3+:[Ar]3d5
_ _ _ _ _
eg t2g
_ _ _
t2g eg
5. [PtCl4]2- Pt2+: [Xe]4f145d8
__

Reactions
1. Labile Complexes: highly reactive
- complexes that undergo rapid ligand exchange reactions
[N i(CN )4 ]2 + 4 CN [N i( CN )4 ]2 + 4CN

2. Inert Complexes
- complexes that undergo very slow ligand exchange reactions (takes hours/days)
[Co(N H3 )6 ]3+ + 6H + + 4H2 O [Co(H2 O)6 ]3+ + 6N H4+
Applications of Coordination Chemistry

- Therapeutic Chelating Agents (EDTA, cis-platine), strongly binds with metals
- Chemical Analysis
- Plant Growth
- Detergents

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The Fundamentals of General Chemistry II

Summer || AY 2010-2011 || Section A

ii | Chemistry 18: Fundamentals of General Chemistry II

2. f (x) = xn f  (x) = nxn1

4. d(uv) = udv + vdu or 1d2, 2d1

 u  vdu udv ldh hdl

Integration: finding the area under the curve

Geoffrey C. Li Notes by A-Log | 1

2 | Chemistry 18: Fundamentals of General Chemistry II

r = correlation coefficient in a calculator: y = A + Bx

y = the value of y when x is... x = the value of x when y is...

rate of appearance of the product = rate of disappearance of the reactant

For the reaction A + 2B C

d[C] d[A] d[B]

[B] is changing at the greatest rate

For the reaction: 3X + 5Y 2Z

[Y] is changing at the greatest rate

[N O2 ] is changing at the greatest rate

Geoffrey C. Li Notes by A-Log | 3

Theories on Reaction Rate

Requirements for an effective collision

rate of reaction frequency of collision

2. Transition State Theory (Henry Eyring)

rate of reaction ease of formation of the transition state

- ease is related with the activation energy

Factors Affecting Reaction Rate

2. Surface Area SA, Rate

3. Concentration of Reactants Concentration, Rate; Rate [reactants]n

Rate Law: k = rate constant

- the order of reaction is experimentally determined

Methods for Determining the Rate Law

[A] [B] Initial Rate (M/s)

rate 3 k(0.020)x (0.010)y rate 2 k(0.010)x (0.020)y

Overall Order: 2+1=3

Double A? 4 Rate Double B? 2 Rate

Rate = k[A]n Plot log Rate vs log [A]

Geoffrey C. Li Notes by A-Log | 5

A: at constant [B] and [C]

Plot log rate vs log [A]

B: at constant [A] and [C]

Plot log rate vs log [B]

C: at constant [A] and [B]

Plot log rate vs log [C]

A: at constant [B] B: at constant [A]

log k[B]y = 2.0315 log k[A]x = 0.67912

Plot log rate vs log [C2 O2

rate = k[HgCl2 ][C2 O42 ]2

From constant [C2 O2

[A]t = kt + [A]0 [A]t

Geoffrey C. Li Notes by A-Log | 7

Summary of Integrated Rate Laws:

t (sec) 0 50 100 150 200

1 4: time when [C5 H6 ]t = (0.20)[C5 H6 ]0

8 | Chemistry 18: Fundamentals of General Chemistry II

1. Given: order = 1 t 12 = 12.0min

ln(0.20)[A]0 = (0.0578 min1 )t + [A]0

Geoffrey C. Li Notes by A-Log | 9

Given: n=1 C8 H18 O2(g) 2C3 H6 O(g) + C2 H6(g)

10 | Chemistry 18: Fundamentals of General Chemistry II

800 x = 4.43 mmHg

4. Temperature Temperature, Rate

2. f (x) = xn f (x) = nxn1

u vdu udv ldh hdl

OCl + H2 O HOCl + OH (fast)