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
GasPhase 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
AcidBase Indicators
44
AcidBase 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 
Calculus Review
2. f (x) = xn
ldh hdl
v
l2
2
4x + 3x 5
Example: f (x) =
2x + 1
5. d
v2
or
f (x) =
6. Chain Rule
f (x) = 2(4x2 7x + 13)(8x 7)
Indefinite Integration
Examples:
x2
+C
1.
xdx =
2
2.
3.
4.
3 dx = 3
dx = 3
5x2 dx = 5
3x2
x dx =
xn+1
n+1
+C
lnx + C
if n = 1
if n = 1
x0 dx = 3x + C
x2 dx =
x
+ 14 dx =
4
5 3
x +C
3
3x2 dx
x
dx +
4
x2
x3
+ 14x + C
3
8
1
= x3 x2 + 14x + C
8
14 dx
=3
5.
10 12
+ 2 dv = 5 dx 10v 1 dx + 12v 2 dx
5
v
v
12 1
v +C
= 5v 10lnv +
1
= 5v 10lnv 12v 1 + C
Geoffrey C. Li
Notes by ALog
 1
b
Definite Integration
f (x) dx
Examples:
4
1.
(x + 2) dx
2
4
x dx +
4
2 dx
4
x
+ 2x
=
2
2
2
2
2
4
+ 2(4)
+ 2(2)
=
2
2
2
= 16 6 = 10
2.
1
1
4x + 2x 3x +
2
1
4x dx +
1
2x dx
dx
1
1
1
3x dx +
1
1
dx
2
x
x
x
1
= 4 + 2 3 + x
4
3
2
2 1
1
3
1
2
= x4 + x3 x2 + x
3
2
2 1
3
1
2
3
1
2
= (1)4 + (1)3 (1)2 + (1) (1)4 + (1)3 (1)2 + (1)
3
2
2
3
2
2
7
=
3
4
3.
2t
t
7t 3 4t1 + 10t2
dt
2t
t2
t1
= 7 3t 4lnt + 10
2
1 t
2t
7
= t2 3t 4lnt 10t1
2
t
7
2
2
(2t) t 3 (2t t) 4 (ln2t lnt) 10 (2t)1 t1
=
2
2t
t
7 2
3t 3t 4 ln 10
=
2
t
2t2
21 2
t 3t 4ln2 5t1
=
2
2 
Example:
x
15
12.5
12
8
13.8
6.7
14.6
y
18
15
14.3
10
16.5
8
17.5
in a calculator: y = A + Bx
A = y int
B = slope
x
= the value of x when y is...
Example: 20
x
r = 0.999228
A = 0.3086
B = 1.176
Equation: y = 1.176x + 0.3086
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
Rate of reaction =
d[A]
1 d[B]
d[C]
=
=
dt
dt
2 dt
d[A]
d[B]
d[C]
(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
if
1 d[X]
1 d[Y ]
1 d[Z]
=
=
2 dt
3 dt
5 dt
1
O2
2
1 d[N O2 ]
d[O2 ]
d[N2 O5 ]
=2
=
Rate of reaction =
2 dt
dt
dt
For the reaction: N2 O5 2N O2 +
Geoffrey C. Li
Notes by ALog
 3
Quiz:
d[N O]
= 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
6 d[N O]
6
d[H2 O]
=
= (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
1 d[N O]
= (0.60M/s) = 0.015M/s
4: Rate of reaction =
4 dt
4
1:
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 constant
p
Z
frequency of collision
Ea
RT
e
Rate [reactants]n
Rate Law:
k = rate constant
rate = k[reactants] n = order of reaction
n
[B]
0.010 M
0.020 M
0.010 M
a. Rate Law
rate = k[A]x [B]y
A:
k(0.020)x (0.010)y
rate 3
=
rate 1
k(0.010)x (0.010)y
x
4.9 104
0.020
=
1.2 104
0.010
B:
k(0.010)x (0.020)y
rate 2
=
rate 1
k(0.010)x (0.010)y
y
4
2.4 10
0.020
=
1.2 104
0.010
2 = 2y
4.08 = 2x
y=1
2
rate = k[A] [B]
x=2
Substitute Experiment 1: k =
= 120 M 2 s1
Double A? 4 Rate
Double B? 2 Rate
b. Differential Method
Rate = k[A]n
Geoffrey C. Li
mx
slope = n
yint = logk
Notes by ALog
 5
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
mx
mx
mx
Example:
[A]
0.020 M
0.020 M
0.020 M
0.020 M
0.025 M
0.030 M
0.035 M
[B]
Initial Rate (M/s)
0.020 M
8.40 105
0.025 M
1.31 104
0.030 M
1.89 104
0.035 M
2.57 104
0.030 M
2.36 104
0.030 M
2.83 104
0.030 M
3.30 104
rate = k[A]x [B]y
A: at constant [B]
log rate = log k[B]y + x log[A]
B: at constant [A]
log rate = log k[A]x + y log[B]
rate = k[A][B]2
log k[B]y = 2.0315
k(0.020) = 100.67912
k(0.030)2 = 102.0315
6 
k = 10.33 M 2 s1
k = 10.47 M 2 s1
Quiz:
[HgCl2 ]
0.164 M
0.164 M
0.164 M
0.164 M
0.082 M
0.041 M
0.021 M
[C2 O2
4 ]
0.15 M
0.45 M
0.90 M
1.80 M
0.45 M
0.45 M
0.45 M
y log[C2 O42 ]
k = 8.54 10
2 1
d[A]
= k[A]n
dt
d[A]
= k[A]1
dt
[A]1 d[A] = k dt
d[A]
= k[A]0
dt
[A]t
t
d[A] = k dt
n=1:
n=0:
[A]0
[A]t
t
1
[A] d[A] = k dt
mx
[A]0
Plot [A] vs t
slope = k
yint = [A]0
[A]t
= k(t 0)
[A]0
ln[A]t ln[A]0 = kt
ln
ln[A]t = kt + ln[A]0
y
mx
Plot ln[A] vs t
slope = k
yint = ln[A]0
Geoffrey C. Li
Notes by ALog
 7
d[A]
= k[A]3
dt
[A]3 d[A] = k dt
d[A]
= k[A]2
dt
[A]2 d[A] = k dt
n=3:
n=2:
[A]t
t
3
[A] d[A] = k dt
[A]t
t
2
[A] d[A] = k dt
0
[A]0
1
1
+
= kt
[A]t
[A]0
1
1
=
kt +
[A]t
[A]0
mx
y
1
1
+
= kt
2[A]2t
2[A]20
1
1
=
kt +
2
2[A]
2[A]2
mx
t
0
y
Plot
[A]0
1
vs t
[A]
slope = k
Plot
1
yint =
[A]0
1
vs t
2[A]2
slope = k
1
yint =
2[A]20
[A]0 = 0.0400 M
t (sec)
[C5 H6 ] (M)
0
0.0400
50
0.0300
100
0.0240
150
0.0200
200
0.0174
1: Order of Reaction
n=0: Plot [A] vs t
n=1: Plot ln [A] vs t
1
vs t
n=2: Plot
[A]
1
vs t
n=3: Plot
[A]2
2: k
rn=0 = 0.967
rn=1 = 0.9905
rn=2 = 0.999776
rn=3 = 0.995
slope = k = 0.163 M 1 s1
3: [C5 H6 ]300
x = t; y =
1
[C5 H6 ]t
1
[C5 H6 ]300
1
= 0.0135 M
[C5 H6 ]300 =
300
y
300
y=
HalfLife t1/2
 time required to reduce the concentration of the reactant to half of its initial value
8 
t = t1 /2 when [A]t =
1
[A]0
2
[A]t = kt + [A]0
1
[A]0 = kt 12 + [A]0
2
1
kt 12 = [A]0 [A]0
2
n = 0: kt 1 = 1 [A]
0
2
2
[A]0
t 12 =
2k
ln
n = 1:
ln[A]t = kt + ln[A]0
1
[A]0 = kt 12 + ln[A]0
2
1
[A]0
kt 12 = ln[A]0 ln
2
[A]0
kt 12 = ln 1
2 [A]0
ln 2
t 12 =
k
t 12 [A]
1
[A]t
1
1
[A]
0
2
1
2
[A]0
[A]0
1
n = 2:
[A]0
t 12 independent of [A]
1
[A]0
1
= kt 12 +
[A]0
= kt +
= kt 12
= kt 12
[A]0
2k
ln 2
n = 1 : t 12 =
k
1
n = 2 : t 21 =
k[A]0
n = 0 : t 12 =
20 s 1
10 s
1
n = 0 : 1M M
2
k[A]0
20 s 1
20 s
n = 1 : 1M M
2
1
20 s 1
40 s
t 12
n = 2 : 1M M
[A]
2
t 12 =
1
5s 1
M M
4
8
1
20 s 1
M M
4
8
1
80 s 1
M M
4
8
Examples:
1. Given: order = 1
12 min
t 12 = 12.0min
12 min
12 min
12 min
t 12 =
ln 2
k
ln 2
= 0.0578 min1
12.0 min
(0.20)[A]0
= (0.0578 min1 )t
[A]0
0
ln (0.20)[A]
[A]0
= 27.84 min
(0.0578 min1 )
c. 10% remaining: [A]t = 0.10[A]0
t=
[A]t
= kt
[A]0
(0.10)[A]0
ln
= (0.0578 min1 )t
[A]0
ln
Geoffrey C. Li
t=
0
ln (0.10)[A]
[A]0
(0.0578 min1 )
= 39.84 min
Notes by ALog
 9
1
1
H2(g) + I2(g)
2
2
[A]5 = 0.68 M
HI(g)
2. Given: order = 2
t=5
[A]0 = 0.90 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
= 0.0719 M 1 min1
k = 0.68 M
5 min
1
1
= (0.0719 M 1 min1 )t +
0.50 M
0.90 M
1
1
0.50 M 0.90 M
= 12.36 min
t=
(0.0719 M 1 min1 )
b. halflife when [HI] is 0.90 M
1
1
=
t 21 =
1
k[A]0
(0.0719 M min1 )(0.90 M )
t 12 = 15.45 min
GasPhase Reactions
t=0
C
t
A
PA,0
x
PA,0 x
n=1
ln
B
0
+x
x
C
0
+2x
2x
PT OT AL = PA + PB + PC
= PA,0 x + x + 2x
= PA,0 + 2x
[A]t
= kt
[A]0
P
RT
Therefore,
ln
PA,t
RT
PA,0
RT
ln
PA,t
= kt
PA,0
= kt
Example:
Given: n=1
t 12 at 147 C = 80 min
PA,600 =?
PA,t
ln 2
= kt
t 12 =
PA,0
k
ln 2
ln 2
k=
= 0.0087 min1
=
t 12
80 min
ln
ln
10 
PA,t
= (0.0087 min1 )(600 min)
800 mmHg
PA,t = (e(0.0087
C8 H18 O2(g)
800 mmHg
x
4.43 mmHg
t=0
C
t
C3 H6 O(g)
0
+2x
2x
C2 H6(g)
0
+x
x
PT OT AL = 4.43 + 2x + x
PT OT AL = 4.43 + 2(795.57) + 795.57 = 2391.14 mmHg
Arrhenius Equation:
k = Ae
Ea
RT
Ea : activation energy
R: ideal gas constant (8.314 J/molK)
k = Ae
Ea
RT
ln k = ln A + ln e
ln k =
y
Ea
RT
Ea 1
+
ln A
R T
b
mx
Plot ln k vs
1
T
Ea
slope =
R
yint = ln A
Ea 1
R T2 + ln A
Ea 1
R
T1 + ln A
Ea
R T12 T11
ln k2 =
ln k1 =
ln kk21 =
y2 y1 = m(x2 x1 )
Example:
T ( C)
k(s1 ) 103
0
0.0106
25
0.319
35
0.986
45
2.92
Find Ea and A:
1
Ea 1
+ ln A
Plot ln k vs
r = 0.999
ln k =
R T
T
Ea
y int = ln A = 28.336
= 10863
slope =
R
A = 2.02 1012
E
=
90319
J
a
Find halflife at 40 C: x =
1
y
ln k =
313.15
ln k = 6.355
1
T
y = ln k
k = 1.738 103 s1
Geoffrey C. Li
t 12 =
ln 2
k
ln 2
1.738 103 s1
= 399 s
Notes by ALog
 11
Quiz
Given: n=2
Ea = 250 kJ/mol
T1 = 838.15 K
t 12 = 25.25 hours
T2 = 973.15 K
t =?
k1 =?
k2 =?
1
1
1
= kt +
t 12 =
[N2 O]t
[N2 O]0
k1 [N2 O]0
1
1
=
= 3.96 M 1 hr1
k1 =
(t 12 )([N2 O]0 )
(25.25 hours)(0.01 M )
k2
Ea 1
1
=
k1
R T2
T1
k2
1
250000 J/mol
1
ln
J
3.96 M 1 hr1
973.15 838.15
8.314 molK
ln
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
I : Catalyst
Uncatalyzed Reaction
OI : Intermediate
Catalyzed Reaction
Higher activation energy than catalyzed Each step has lower activation energy than
the uncatalyzed
Has only one transition state
Has no intermediate
12 
Transition State
Intermediate
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
k
NO2 + NO2
k2
CO + NO3
CO + NO2
Rate = k [NO2 ]2
NO3 + NO
(slow)
CO2 + NO2
CO2 + NO
(fast)
elementary steps
slowest step
 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
Mechanism 1
NO + Cl2
NO + NOCl2
2NO + Cl2
k2
NOCl2
(slow)
2NOCl
2NOCl
(fast)
Geoffrey C. Li
Notes by ALog
 13
Mechanism 2
NO + Cl2
NO + NOCl2
2NO + Cl2
NOCl2
2NOCl
2NOCl
(fast)
(slow)
[N OCl2 ]
[N O][Cl2 ]
=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])
[N OCl2 ] =
Rate =
k1 [N O][Cl2 ]
k1 + k2 [N O]
k2 k1 [N O]2 [Cl2 ]
k1 + k2 [N O]
If k1 >>> k2 k1 + k2 [N O] k1
k2 k1 [N O]2 [Cl2 ]
k2 k 1
=
[N O]2 [Cl2 ]
k1
k1
Holds with experimental rate law
Rate =
If k2 >>> k1 k1 + k2 [N O] k2 [N O]
k2 k1 [N O]2 [Cl2 ]
= k1 [N O][Cl2 ]
k2 [N O]
Does not hold with experimental rate law
This means that rate2 < rate1
Rate =
Example 2:
Overall Reaction: A + 2B C
A+A
A2 + B
AB + B
A + 2B
A2
AB + A
C
C
(fast)
(slow)
(fast)
14 
Equilibrium Method:
K=
[A2 ]
[A]2
[A2 ] = K[A]2
Rate = k2 [B]K[A]2
Rate =
k1 [A]2
k1 + k2 [B]
k2 k1 [A]2 [B]
k1 + k2 [B]
If k1 >>> k2 k1 + k2 [B] k1
k2 k1 [A]2 [B]
k 2 k1 2
=
[A] [B]
k1
k1
Holds with experimental rate law
Rate =
k2 k1 [A]2 [B]
= k1 [A]2
k2 [B]
Does not hold with experimental rate law
This means that rate2 < rate1
Rate =
1. Chain initiation:
radical: with unpaired electron
Br2 + light 2Br
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
Cl + O3
ClO + O
O3 + O
Geoffrey C. Li
CF2 Cl + Cl
O2 + ClO
O2 + Cl
2O2
(chain initiation)
(chain propagation)
(chain propagation)
Notes by ALog
 15
Quiz
Overall Reaction: I + OCl OI + Cl
OCl + H2 O
I + HOCl
HOI + OH
I + OCl
HOCl + OH
HOI + Cl
H2 O + OI
OI + Cl
(fast)
(slow)
(fast)
Equilibrium Method:
K=
[HOCl][OH ]
[OCl ]
[HOCl] =
K[OCl ]
[OH ]
[HOCl] =
k2 k1 [I ][OCl ]
k1 [OH ] + k2 [I ]
k1 [OCl ]
k1 [OH ] + k2 [I ]
k2 k1
[I ][OCl ][OH ]1
k1
>>> k1 , Rate = k1 [OCl ]
If k1 >>> k2 , Rate =
If k2
Nuclear Chemistry
Chemical Reactions
Nuclear Reactions
formation/breaking of bonds
valence electrons
Energy change
lower
higher
16 
proton: 11 p or 11 H
electron:
0
1 e
neutron: 10 n
p, n, n\p ratio
234
234
0
1
1
0
Example: 90 U 91 P a +1 e 0 n 1 p +1 e
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
Example: 15 P 14 Si +1 e
10 n +01 e
40
0
40
Example: 19 K +1 e 18 Ar
1
1p
1
1p
+01 e 10 n
Example:
238
92 U
236
92 U
234
90 T h
234
91 U
234
92 U
230
90 T h
207
232
82 P b 92 U
206
82 P b
208
82 P b
Kinetics of Radioactive Decay
 all obey firstorder 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
k
0
Geoffrey C. Li
Notes by ALog
 17
Example:
t 12 = 12.8 hrs
N = 1.50 mg
t = 48 hrs
1 mol
6.02 1023 disintegrations
1 hr
ln 2
1g
activity = kN =
(mg)
t 12
1000 mg
64 g
1 mol
3600 s
23
1g
1 mol
6.02 10 disintegrations
1 hr
ln 2
(1.50 mg)
=
12.8 hrs
1000 mg
64 g
1 mol
3600 s
1
Ci
= 5741 Ci
= 2.12 101 4 Bq
3.7 1010 Bq
Nt
= kt
N0
Nt = ekt (N0 )
ln
Nt = e(0.0542
hr 1 )(48 hrs)
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
atomic mass = 27.96924
14 Si
1.00728 amu
proton
+ 14 neutrons
1.00867 amu
neutron
= 28.22330 amu
1 kg
1g
= 3.798 1011 J
6.02 1023 amu
1000 g
3.798 1011 J
= 1.357 1012 J/nucleon
nuclear binding energy per nucleon =
28 nucleons
18 
Quiz
activity0 = 0.0500 Ci
Nt
= kt
ln
N0
k=
ln
activityt
k
activity0
k
t
k = 0.159 hr1
activityt = 0.0310 Ci
t = 30.0 hrs
0.0310 Ci
ln 0=0.0500
Ci
30.0 hrs
ln 2
k
ln 2
ln 2
=
= 43.5 hours
t 12 =
k
0.159 hr1
t 12 =
N96 :
ln
Nt
= (0.159 hr1 )(96 hours) = 1.5624
N0
Nt
= 0.2166 remaining
N0
56
26 F e
78.34% disintegrated
1.00728 amu
proton
+ 30 neutrons
1.00867 amu
neutron
= 56.44938 amu
1 kg
1g
= 7.904 1011 J
6.02 1023 amu
1000 g
7.904 1011 J
= 1.41 1012 J/nucleon
nuclear binding energy per nucleon =
56 nucleons
Examples:
14
7 N
1
+42 He 17
8 O +1 H
9
4 Be
1
+42 He 12
6 C +0 n
Transuranium Elements
 manmade elements, prepared from Uranium
 located after Uranium in the periodic table
238
Example: 1st Transuranium element to be discovered: 92 U (n, )
238
1
239
0
92 U +0 n 93 N p +1 e
239
93 N p
+10 n
142
56 Ba
1
+91
36 Kr + 30 n
Geoffrey C. Li
Notes by ALog
 19
4
2 He
H2 O H2 O+ + e
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
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
energy = 9.1210
13
time = 2 hours
J/disintegration
85% absorbed
RBE = 1
3.7 1010 Bq
= 3.3 109 Bq
Activity in Bq = 90 mCi
1 Ci
3.3109 disintegrations
9.121013 J
(7200
s)
1 s
1disintegration (0.85)
Absorbed Dose =
= 0.246 Gy
75 kg
100 rad
0.246 Gy
= 24.6 rad
1 Gy
1 Ci
1000 mCi
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
20 
Intensive Property =
Extensive Property 1
Extensive Property 2
() q
() w
(+) q
() q
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
CV
CP
monoatomic
diatomic
3
R
2
5
R
2
5
R
2
7
R
2
C P = CV + R
Geoffrey C. Li
Notes by ALog
 21
Work, w
w = F dx
F
A
F = PA
A dx = dV
A: crosssectional area
P: external pressure
w = P dV
P dV
 the negative sign is added to follow direction, it has no bearing on the magnitude
wirrev =
Pext dV
Irreversible Work
SingleStep: from V1 to V2 in one pressure change
TwoStep:
from V1 to V2 in two pressure changes
ThreeStep:
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 OneStep < Work in TwoStep < Work in ThreeStep < < Work in InfiniteStep
Reversible Work
U = q + w
Ideal Gas Systems (dependent on path)
1. Isobaric (Constant Pressure)
qP = nCP T
wirrev = Pext dV
wrev =
Pgas dV = Pgas
V2
U = q + w
= nCP T nRT
= n(CP R)T
dV
= nCV T
V1
= P V = nRT
qV = nCV T
wirrev = 0
22 
wrev = 0
U = q + w
=q
= nCV T
Chemistry 18: Fundamentals of General Chemistry II
3. Isothermal (Constant T)
U = 0
wirrev =
U = q + w
0=q+w
q = w
wrev =
V2
Pext dV
Pgas dV
nRT
dV
V
V1
V2
dV
V
= nRT ln
V2
V1
= nRT
V1
4. Adiabatic
q=0
U = q + w
U = w
U = nCV T
Example
Given:
Helium Gas
wrev =?
n = 3 moles
q=?
A: at constant P
qP = nCP T
qP = (3 mol)
Tf = 100 K
U=?
J
5
8.314
2
molK
qP = 4676.63 J
V2
wrev = Pgas dV
Ti = 25 K
Assume He is an ideal gas
(100K 25K)
U = q + w
U = 4676.63 J + 1870.65 J
U = 2805.98 J
V1
wrev = Pgas
V2
V1
wrev
dV = P V = nRT
J
= (3 moles) 8.314
molK
wrev = 1870 J
(75K)
U = nCV T
U = (3 moles)
U = 2805.98 J
B: at constant V
wrev = 0
qV = nCV T
qV = (3 mol)
J
3
8.314
2
molK
(75K)
U = q + w
U = q + 0 = q
qV = 2805.98 J
Geoffrey C. Li
J
3
8.314
2
molK
U = 2805.98 J
(100K 25K)
Notes by ALog
 23
Isocoric: H = U + (P V )
U = qp + w
= nCV T + nRT
= n(CV + R)T
U = H + w
H = U w
= nCP T
H = U (P V )
H = U + P V
H: enthalpy = U + P V
Isothermal: H = 0
Adiabatic: H = nCP T
Example:
Given:
N2(g)
Assume N2(g) is ideal
n = 2 moles
T = 303.15 K
A: reversible
H = 0
wrev =
Vf = 4L
Vi = 2L
U = 0 (isothermal system)
V2
Pgas dV =
V1
V2
nRT
dV
V
V1
wrev = nRT
V2
V1
V2
dV
= nRT ln
V
V1
wrev = (2moles)(8.314
4L
J
)(303.15K) ln
molK
2L
wrev = 3494 J
q = w
q = 3494 J
U = 0 (isothermal system)
V2
Pext dV = Pext
V1
V2
dV
V1
q
wirrev
24 
J
8.314 molK
= 405.26 J
Latm
0.08206 molK
Isobaric
Isocoric
Isothermal
qP = nCP T
Pext dV
qV = nCV T
q = w
Pext dV
Adiabatic
0
Pext dV
Isobaric
Isocoric
Isothermal
wrev
P V = nRT
nCV T
nCV T
w = nCV T
nCP T
nCP T
nCP T
nRT ln
Adiabatic
Pgas dV
V2
V1
Quiz
Given:
O2(g)
adiabatic (q=0)
wirrev =
V2
n = 2 moles
Pgas = 4.50 atm
Pext dV = Pext
wirrev
wirrev
dV
nRT
P
= Pext (V2 V1 )
Latm
2 mol 0.08206 molK
313.15K
V1 =
1 atm
4.50
atm
(34.26L 11.42L)
= 800 torr
760 torr
V1 = 11.42L
J
8.314 molK
= 24.04 Latm
= 2435.85 J
Latm
0.08206 molK
V = 3V = 3(11.42L)
V1
wirrev
V2
T1 = 313.15 K
Pext = 800 torr
V1 =
V1
V2 = 34.26L
U = q + w = 0 + w = w
U = 2435.85 J
U = nCV T
2435.85 J = (2 mol)
5
J
8.314
2
molK
T2 = 254.55 K
(T2 313.15 K)
Thermochemistry
 measurement and calculation of heats of reaction at constant pressure
 H is measured
H = qP
H = U + PV
H = U + (P V )
endothermic: H > 0
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
C4 H10(l) + O2(g) 4CO2(g) + 5H2 O(l)
2
ng = 4
13
5
=
2
2
Hrxn = Urxn + ng RT
5
J
1 kJ
kJ
Hrxn = 2648
+
8.314
(298.15 K)
mol
2
molK
1000 J
kJ
Hrxn = 2654.20
mol
Geoffrey C. Li
Notes by ALog
 25
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
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:
m = 1.800 g
T1 = 21.36 C
qtotal = 0
qcombustion + qcal = 0
qcombustion = qcal = Ccal T
U =
H = U + ng RT
average temp: 298.15 K
kJ
J
1 kJ
+ (1) 8.314
(298.15 K)
mol
molK
1000 J
kJ
H = 3057.20
mol
H = 3054.72
2C(s,
graphite)
1
+ 3H2(g) + O2(g) C2 H5 OH(l)
2
Ca(s) + Cl2(g) CaCl2(s)
3
N2(g) + 2H2(g) + O2(g) N H4 N O3(g)
2
kJ
mol
kJ
Hf = 795.8
mol
kJ
Hf = 365.6
mol
Hf = 277.7
Hf,
elements = 0
Hf,
N2(g) = 0
Hf,
=0
O2(g)
Hf,
Cl2(g)
=0
Hf,
Br2(g)
Hf,
Cgraphite
Hf,
Cdiamond
13
O2(g) 4CO2(g) + 5H2 O(l)
2
Hrxn = nHf , products nHf , reactants
kJ
kJ
= (4 mol) 393.5
+ (5 mol) 285.83
mol
mol
kJ
13
kJ
(1 mol) 124.73
+(
mol) 0
mol
2
mol
C4 H10(g) +
= 2878.42kJ
A
B
C
A
solid
liquid
solid
B
C
D
D
H1
H2
H3
H = H1 + H2 + H3
liquid
gas
gas
Hf us
Hvap
Hsub
Hsub = Hf us + Hvap
Example
4N H3(g) + 3O2(g) 2N 2(g) + 6H2 O(l)
N2 O(g) + H2(g) N 2(g) + H2 O(g)
1
H2(g) + O2(g) H2 O(l)
2
Geoffrey C. Li
kJ
mol
kJ
H = 367.4
mol
kJ
H = 285.9
mol
H = 1531
Notes by ALog
 27
kJ
1
1531
2
mol
kJ
H = 3 367.4
mol
kJ
H = 3 285.9
mol
1
[4N H3(g) + 3O2(g) 2N 2(g) + 6H2 O(l) ]
2
H =
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:
C4 H10(g) +
13
O2(g) 4CO2(g) + 5H2 O(g)
2
C4 H10(g) + 13
2 O2(g)
5H2 O(g)
C4 H10(g) + 13
2 O2(g)
H = 2630.5 kJ
H = 5(44.01 kJ)
H = 2850.55 kJ
Measuring Hrxn using standard heats of formation is more reliable than using bond enthalpies since bond enthalpies change according to the environment of the bond.
Quiz
Given:
C8 H18
T2 = 66.5 C
28 
V = 10.00 mL
T1 = 23.2 C
= 0.688 g/mL
Average = 25 C
qtotal = 0
qcomb + qcal = 0
qcomb = qcal
= Ccal T
kJ
7.62
(66.5 C 23.2 C)
C
= 329.946 kJ = qv
U =
329.946 kJ
kJ
0.688 g 1 mol = 5467.21 mol
(10.00 mL) 1 mL
114 gC H
8
18
9
25
25
O2(g) 8CO2(g) + 9H2 O(l)
=
ng = 8
2
2
2
H = U + ng RT
kJ
kJ
9
8.314 103
(298.15 K)
= 5467.21
mol
2
molK
kJ
= 5478.36
mol
C8 H18(g) +
mol) 0
(1 mol) Hf, C8 H18 + (
2
mol
kJ
Hf,
C8 H18 = 242.11
mol
dS =
dqrev
T
S>0
S>0
S<0
S<0
 being an isolated system is important (no exchange between system and surroundings)
 we can treat the whole universe as an isolated system
Suniverse > 0
Ssys + Ssurr > 0
Geoffrey C. Li
Notes by ALog
 29
nCP dT
dqP
=
T
T
T
S
2
2
nCP dT
dS =
T
nCV dT
dqV
=
T
T
T
S
2
2
nCV dT
dS =
T
dS =
S1
T1
S = nCP ln
dS =
T2
T1
S1
T1
S = nCV ln
T2
T1
3. Isothermal 4. Adiabatic
dwrev
dqrev
dS = 0
=
T
T
Pgas dV
(Pgas dV )
=
=
T
T
nRT
dV
dV
= nR
= V
T
V
S2
S2
dV
S = nR
V
dS =
S1
S1
S = nR ln
V2
V1
S =
qrev
Htransition
=
T
Ttransition
Chemical Reactions
Srxn
= nSprod
nSreac
Selements
= 0
Example
Given:
H2 O(s) H2 O(g)
P = 1 atm
n = 2 moles
Tf = 383.15 K
Hvap,
water
Ti = 268.15 K
= 40.67 kJ/mol
30 
273.15 K
T2
J
S1 = nCP ln
= (2 mol) 37.7
ln
T1
molK
268.15 K
J
= 1.39
K
S2
S3
S4
S5
kJ
(2 mol) 6.02 mol
nHf us
=
=
Tm
273.15 K
J
= 44.08
K
373.15
T2
J
ln
= nCP ln
= (2 mol) 75.3
T1
molK
273.15
J
= 46.98
K
kJ
(2 mol) 40.67 mol
nHvap
=
=
Tb
373.15 K
J
= 217.98
K
383.15
T2
J
ln
= nCP ln
= (2 mol) 33.9
T1
molK
373.15
J
= 1.79
K
K
K
K
K
ST = S1 + S2 + S3 + S4 + S5
J
= 312.22
K
Quiz
Given:
Hf us = 9.87 kJ/mol
Hvap = 30.7 kJ/mol
liquid CP = 136.1 J/molK
gas CP = 84.67 J/molK
Ti = 278.75K
Svap =
Hvap
Tb
Tb =
J
30700 mol
Hvap
=
= 353.28 K
J
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
Suniverse > 0
Ssystem + Ssystem
qsys
Ssys
T
T Ssys qsys
T Ssys Hsys
at constant P, qP = H
Hsys T Ssys
Gsys
>0
>0
>0
>0
<0
<0
G=
H
heat available
Geoffrey C. Li
TS
heat used
G = H T S
Notes by ALog
 31
G < 0: spontaneous
G = 0: equilibrium
G > 0: nonspontaneous
Example:
Hf us
6.02 kJ/mol
=
Tm
273.15 K
kJ
= 0.02204
molK
Hf us = 6.02 kJ/mol
Sf us =
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
(263.15K) 0.02204
= 0.2204
mol
molK
mol
at 10 C : G = 6.02
2.
NONSPONTANEOUS at 10
Hf
S
6CO2(g)
393.5
213.6
+6H2 O(l)
285.83
69.91
C6 H12 O6(s)
1273.02
212.1
+6O2(g)
0
205.0
kJ/mol
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 =
+
+
T S
+
Reaction
Reaction
Reaction
Reaction
is
is
is
is
spontaneous at all T
spontaneous at low T
spontaneous at high T
nonspontaneous at all T
elements
=0
32 
kJ
q = nHvap = (2 mol) 40.67
= 81.34 kJ
mol
V2
dV = Pext (V2 V1 )
V1
Assume Vgas >>> Vliq ; for liquid to solid reactions use density to convert
= P Vgas = nRT
J
(373.15 K) = 6205 J
= (2 mol) 8.314
molK
U = q + w
Spure,
crystalline, solid at 0K
=0
0K 298.15K
S = S298.15K S0K
S = S298.15K
q
wirrev
Isobaric
Isocoric
Isothermal
qP = nCP T
Pext dV
qV = nCV T
q = w
Pext dV
Adiabatic
0
Pext dV
wrev
P V = nRT
V2
nRT ln
V1
nCV T
nCV T
w = nCV T
nCP T
nCP T
nCP T
nCP ln
T2
T1
nCV ln
T2
T1
nR ln
V2
V1
Pgas dV
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
Geoffrey C. Li
Notes by ALog
 33
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
aN O 2
G = G + RT ln
1
aN2 2 aO2
Q: reaction quotient
aN O 2
Qa =
1
aN2 2 aO2
at equilibrium:
G = 0
0 = G + RT ln Ka
G = RT ln Ka
G
ln Ka =
RT
K a = e
aN O2
Ka =
G
RT
aN2 2 aO2
PN O2
1
2
N O2
1
2
N2 O2
(PN2 ) PO2
Ka = K KP
CRTN O2
1
2
CRTN2 CRTO2
KP = KC (RT )
34 
kJ
mol
PN O2
1
2
PN2 2 PO2
CN O 2
CN2 CO2
P =
nRT
= M RT = CRT
V
1
(RT ) 2
ng
Example
Gf,N O2(g) = 51.84
T = 298.15K
1
N2(g) + O2(g) N O2(g)
2
G
RT
51.84 kJ
(8.314103 kJ/molK)(298.15 K)
= 8.27 1010
since the gases are ideal,
Ka = KP = 8.27 1010
KP = KC (RT )ng
KC =
KP
8.27 1010
=
1
n
(RT ) g
[(8.314 103 kJ/molK)(298.15 K)] 2
= 4.09 109
Manipulating Equations
1
N2(g) + O2(g) N O2(g)
2
1
2 N2(g) + O2(g) N O2(g)
2
1 1
N2(g) + O2(g) N O2(g)
2 2
1
1 N2(g) + O2(g) N O2(g)
2
KP = 8.27 1010
KP = (8.27 1010 )2
1
KP = (8.27 1010 ) 2
KP = (8.27 1010 )1
Adding/Subtracting
1
2 N2(g)
Quiz
+ O2(g)
N O(g)
N O(g) + 12 O2(g)
O2(g)
1
1
2 N2(g) + 2 O2(g)
N O2(g)
KC1
KC2
KC1 KC2
KP = 1 1030
1
[2N O(g) N2(g) + O2(g) ]
2
3
1
[3N O(g) + Br2(g) 3N OBr(g) ]
3
2
(KP = 1 1030 ) 2
Overall:
KP = 715.5
1
1
1
N2(g) + O2(g) + Br2(g) N OBr(g)
2
2
2
G = RT ln Ka
(KP = 715.5) 3
KP = 8.944 1015
Ka KP
kJ
mol
Molecular Equilibrium
Solving Equilibrium Problems
1. Write the balanced equilibrium equation
Geoffrey C. Li
Notes by ALog
 35
2. ICE table
3. Relate equilibrium concentrations to K
4. Solve
Homogenous Equilibria
1. Given:
1 mol SO3(g)
I
C
E
2L vessel
2SO3g
0.5 M
0.0625 M
0.4375 M
303.15 K
2SO2g
2M
+0.0625 M
0.0625 M
O2g
0M
+(0.5)0.0625 M
0.03125 M
[SO2 ]2 [O2 ]
[SO3 ]2
(0.0625M )2 (0.03125M )
KC =
(0.4375M )2
KC =
KC = 6.38 104
KP = KC (RT )
ng
= 6.38 10
KP = 0.0159
Latm
0.08206
molK
(303.15 K)
2. Given:
PN O = 300 mmHg
I
C
E
NO(g)
300
x
300x
+ O2(g)
(0.5)x
2500.5x
T = 473.15 K
NOCl(g)
0M
+x
x
KP =
PN OCl
1
2
PN O PCL
2
260/760
KP =
(140/760)(120/760) 2
KP = 16.36
KC =
KP
16.36
=
1
n
g
(RT )
Latm
0.08206 molK
(473.15 K) 2
KC = 101.94
36 
N2
0
+0.05
0.05
3H2
0
+0.15
0.15
PT = 2 atm
0.3 mol
2 atm = 1.2 atm
0.5mol
0.05 mol
2 atm = 0.2 atm
= N 2 PT =
0.5mol
0.15 mol
2 atm = 0.6 atm
= H 2 PT =
0.5mol
P N H 3 = N H 3 PT =
PN2
PH2
KP =
3
PN2 PH
(0.2)(0.6)3
2
=
= 0.030
2
P N H3
(1.2)2
QUIZ
Given: Initial: 0.112 mol O2 0.0400 mol N2 O in 2.00L
I
C
E
2N2 O(g)
0.02 M
 0.01
0.01 M
3O2(g)
0.56 M
 0.015
0.041 M
4NO2(g)
0
+ 0.02
0.02 M
KC =
I
C
E
At Equilibrium:
CO(g)
0
+x
x
[N O2 ]4
(0.02)4
=
= 23.21
[N2 O]2 [O2 ]3
(0.01)2 (0.041)3
KC = 8 at 298.15 K
Cl2(g)
0
+x
x
[COCl2 ] = 0.002 M
[CO][Cl2 ]
[COCl2 ]
x = 0.123
8=
KC =
[CO] = 0.123 M
x2
0.125 x
[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
KC = [N H3 ][HCl]
KC =
KP =
KC =
[H2 ]
[H2 O]
1
0.5
PO
2
[CO]2
[CO2 ]
NH4 Cl(s)

NH3(g)
0
+x
x
HCl(g)
0
+x
x
PT = 450 mmHg = 2x
x = 225 mmHg
KP = PN H3 PHCl =
KC =
225
760
2
= 0.0876
KP
0.0876
=
= 1.46 104
n
g
(RT )
[(0.09206)(298.15)]2
Geoffrey C. Li
Notes by ALog
 37
NH4 HS(s)

NH3(g)
0
+y
y
H2 S(g)
0
+y
y
KC = [N H3 ][H2 S]
1.2 104 = y 2
y = 0.011 M
[H2 S]=0.011 M
CCl4(g)
0.15 M
z
0.15  z
C(s)

2Cl2(g)
0.005 M
+ 2z
0.005 + 2z
KC = 0.0132 at 700 K
[Cl2 ]2
[CCl4 ]
z = 0.0183
KC =
0.0132 =
(0.005 + 2z)2
0.15 z
[Cl2 ] = 0.0416 M
1. Concentration
 changes in concentration of solids and pure liquids do not affect equilibrium
3. Temperature
 alters the value of the rate constant
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
G = RT ln K + RT ln Q
Q
G = RT ln
K
38 
COCl2(g)
0.5 M
a
0.5  a
CO(g)
0
+a
a
KC = 8
Cl2(g)
0
+a
a
I
C
E
I
C
E
I
C
E
COCl2(g)
0.028 M
+ 0.5
0.528
COCl2(g)
0.028 M
CO(g)
0.472
[CO][Cl2 ]
[COCl2 ]
a = 0.472
KC =
[CO] = 0.472 M
Cl2(g)
0.472
COCl2(g)
0.028 M
+b
0.028 + b
CO(g)
0.472 M
b
0.472  b
[Cl2 ] = 0.472 M
(0.472)2
[CO][Cl2 ]
=
= 0.422
[COCl2 ]
0.528
KC > Qc (forward shift)
Cl2(g)
0.472
+ 0.5
0.972
+
a2
0.5 a
QC =
CO(g)
0.472
8=
(0.472)(0.972)
[CO][Cl2 ]
=
= 16.39
[COCl2 ]
0.028
KC < Qc (backward shift)
QC =
Cl2(g)
0.972 M
b
0.972  b
[CO][Cl2 ]
[COCl2 ]
(0.472 b)(0.972 b)
8=
0.028 + b
b = 0.0249
KC =
[CO] = 0.4471 M
[Cl2 ] = 0.9471 M
Temperature: alters K
G = RT ln Ka
H T S
G
=
ln Ka =
RT
RT
S
H 1
+
(vant Hoff equation)
ln Ka =
R
T
R
1
T
slope: Endothermic: S
yint:
R
Plot lnKa vs
Twopoint form:
ln
H
Ka2
=
Ka1
R
1
1
T2
T1
Exothermic: +
Ionic Equilibria
Geoffrey C. Li
Notes by ALog
 39
Examples: CH3COOH (weak acid), NH3 (weak base), AgCl (partially soluble)
Theories on Acids and Bases
Arrhenius
Acid: H+ producers
+
N H3(aq) + H2 O(l) N H4(aq)
+ OH(aq)
BronstedLowry
Acid: H+ donors
Bases: H+ acceptors
base 2
acid 2
+
N H4(aq)
N H3(aq) + H2 O(l)
base 1
acid 2
base 1
+ OH(aq)
acid 1
+
N H4(aq)
HCl(aq) + N H3(aq)
base 2
+ 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
 forms coordinate covalent bonds (only one atom donates the electron pair)
 not all Lewis acids are BronstedLowry 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 BronstedLowry theory)
1. Polarity of the HX bond
 having the greatest protonlike characteristics (most positive)
2. Strength of the HX 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 HX bond / electronegativity
 HF has the most protonlike H+ (most positive)
From TOP TO BOTTOM: Acidity INCREASES
40 
KW = [H3 O+ ][OH ]
at 298.15 K, pure water, KW = 1.0 1014
at 298.15 K,
pH + pOH = pKw
at 298.15 K, pH + pOH = 14
pOH > 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
Geoffrey C. Li
Notes by ALog
 41
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 =
[H3 O+ ][A ]
[HA]
Kb =
[BH + ][OH ]
[B]
Polyprotic Acids
+
+
H2 P O4(aq) + H2 O(l) H3 O(aq) + HP O4(aq)
2
+
3
HP O4(aq)
+ H2 O(l) H3 O(aq)
+ P O4(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
KN O3(aq)
N a+
(aq)
from a strong base
no hydrolysis
F(aq)
from a weak acid
F(aq)
+ H2 O(l) HF(aq) + OH(aq)
(Kb )
pH > 7
+
N H4(aq)
from a weak base
+
+
N H4(aq)
+ H2 O(l) H3 O(aq)
+ N H3(aq) (Ka )
pH < 7
Cl(aq)
from a strong acid
no hydrolysis
More Examples:
42 
neutral
neutral
basic
acidic
basic
acidic
A
(aq) + H2 O(l) HA(aq) + OH(aq)
[HA][OH ] [H3 O+ ]
[A ]
[H3 O+ ]
[HA]
Kb =
[OH][H3 O+ ]
[A ][H3 O+ ]
1
KW
Kb =
Ka
Kb =
 this also explains why when an acid is very strong, its conjugate base is weak
+
N H4(aq)
from a weak base
+
+
N H4(aq)
+ H2 O(l) H3 O(aq)
+ N H3(aq) (Ka )
Ka > Kb
Ka = Kb
Ka < Kb
Kb : N H3 = 1.8 105
Ka : N H4+ = 5.56 1010
F(aq)
from a weak acid
F(aq)
+ H2 O(l) HF(aq) + OH(aq)
(Kb )
acidic salt
neutral salt
basic salt
>
acidic salt
Ka : HF = 6.8 104
Kb : F = 1.47 1011
Amphoteric Compounds
+
+
2
HCO3(aq)
+ H2 O(l) H3 O(aq)
+ CO3(aq)
N aHCO3 N a+
(aq) + HCO3(aq)
Ka1
Ka2
HCO3 is amphoteric
+
2
+ H2 O(l) H3 O(aq)
+ CO3(aq)
HCO3(aq)
HCO3(aq)
+ H2 O(l) H2 CO3(aq) + OH(aq)
+
H2 P O4(aq)
+ H2 O(l) H3 O(aq)
+ HP O4(aq)
2
+
3
HP O4(aq) + H2 O(l) H3 O(aq) + P O4(aq)
Notes by ALog
 43
pH
0.10 M HCl
100%
1.0
100%
1.0
0.10 M HOAc
1.34%
2.87
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)
Ka =
[H3 O+ ][A ]
[HA]
[A ]
[HA]
[A ]
log[H3 O+ ] = log Ka + log
[HA]
pH = pKa + log
[A ]
(HendersonHasselbalch Equation)
[HA]
[BH + ]
[B]
+ 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)
AcidBase 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.
[In ]
[HIn]
[HIn]
[In ]
10
10
pH range
+1
pKa
1
AcidBase Titration
 technique used to determine the concentration of an acid or base, using a known concentration of a known base or acid
+
Ag(aq)
+ 2N H3(aq) Ag(N H3 )+
2(aq)
Kf : formation constant
Kf =
[Cu(N H3 )2+
4 ]
2+
[Cu ][N H3 ]4
= 5 1013
Kf : formation constant
Kf =
[Ag(N H3 )2+
2 ]
= 1.7 107
+
[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)
KSP = [P b2+ ][I ]2 = 1.4 108
Ksp = solubility product constant
3+
Al(OH)3(s) Al(aq)
+ 3OH(aq)
 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
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)
Geoffrey C. Li
Notes by ALog
 45
2+
M g(OH)2(s) M g(aq)
+ 2OH(aq)
+
2H2 O(l)
OH(aq)
+ H3 O(aq)
Exceptions:
Ksp
CuS
6 1037
CdS
8 1028
P bF2(s) P b2+
(aq) + 2F(aq)
+
HF(aq) + H2 O(l)
F(aq)
+ H3 O(aq)
PbS
3 1028
NiS
3 1020
FeS
6 1019
ZnS
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)
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
2
BaCO3(s) Ba2+
(aq) + CO3(aq)
2
+
CO3(aq)
+ H3 O(aq)
HCO3(aq)
+ H2 O(l)
+
HCO3
(aq) + H3 O(aq) H2 CO3(aq) +H2 O(l)
CO2 +H2 O
Amphoteric Hydroxides
 soluble on both acids and bases
+
3+
Al(OH)3(s) + 3H3 O(aq)
Al(aq)
+ 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 reductionoxidation reactions
46 
Electrochemical Cell
 cells that harness electrical energy from chemical energy in solution
Example: Daniell Cell
Electrode potential
 cannot be exactly determined
 measured using a reference electrode
 Standard Hydrogen Electrode (SHE)
Geoffrey C. Li
+
2H(aq)
+ 2e H2(g)
E = 0V
 47
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
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 > Cr2O724. 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. ZnZn2+ N i2+ N i
Anode:
Cathode:
Cell Reaction:
[Zn2+ + 2e Zn(s) ]
N i2+ + 2e N i(s)
Zn(s) + N i2+ N i(s) + Zn2+
E = 0.76V
E = 0.25V
= Ecathode
Eanode
Ecell
Ecell = 0.51V
> 0, Galvanic
Ecell
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. AgAg + F e2+ F e
Anode:
Cathode:
Cell Reaction:
2[Ag + + e Ag(s) ]
F e2+ + 2e F e(s)
2Ag(s) + F e2+ F e(s) + 2Ag +
E = 0.80V
E = 0.44V
= 1.24V
Ecell
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
2[Cr3+ + 3e Cr(s) ]
3[Cl2(g) + 2e 2Cl ]
3+
3Cl2(g) + 2Cr(s) 6Cl(aq)
+ 2Craq
E = 0.74V
E = 1.36V
Ecell
= 2.10V
E = E
at 25 C, E = E
J
8.314 molK
298.15 K
2.303 log Q
C
n 96485 mol
0.0592
log Q
n
E = E
Nernst Equation
(at 25 C)
Anode:
Cathode:
Cell Reaction:
E = 0.13V
E = 1.82V
= 1.95V
Ecell
[P b2+ ][Co2+ ]2
0.0592
log
n
[Co3+ ]2
(0.010)(0.0040)2
0.0592
log
= 1.95V
= 2.07V
2
(0.050)2
Ecell = Ecell
Ecell
Anode:
Cathode:
Cell Reaction:
Ecell = Ecell
Cr2 O72
E = 0.34V
E = 1.33V
Ecell
= 0.99V
[Cu2+ ]3 [Cr3+ ]2
0.0592
log
n
[Cr2 O72 ][H + ]14
Ecell = 0.99V
(0.50)3 (0.080)2
0.0592
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
K=e
nF E
RT
K = 10
nE
0.0592
at 25 C
Example:
1. P b(s) + 2CO3+ P b2+ + 2Co2+
Find K
K = 10 0.0592 = 10
Geoffrey C. Li
21.95V
0.0592
= 7.56 1065
Notes by ALog
 49
Find K
[M g 2+ + 2e M g(s)]
2H + + 2e H2(g)
M g(s) + 2H + M g 2+ + H2(g)
E = 2.37V
E = 0V
= 2.37V
Ecell
22.37V
AgCl(s) Ag(aq)
+ Cl(aq)
Anode:
Cathode:
Cell Reaction:
nE
[Ag + + e Ag(s)]
Ksp = 10 0.0592 = 10
10.58V
0.0592
E = 0.80V
E = 0.22V
Ecell
= 0.58V
= 1.59 1010
Quiz
P tF e3+ (1.20M ), F e2+ (0.0075M )M nO4 (0.0020M ), H + , M n2+ (2.50M )P t
Anode:
Cathode:
Cell Reaction:
M nO4 + 8H + 5e M n2 + 4H2 O]
5F e3+
E = 0.77V
E = 1.51V
Ecell
= 0.74V
log
> 0.74
5
[H + ]8
0.0592
1.31072 1014
< 62.5
log
[H + ]8
1.31072 1014
log
< [H + ]8
3.162 1062
[H + ] > 8.96 107 M
pH < 6.05
Ecell = Ecell
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, AgAg+
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
50 
 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
2. Reaction occurs at the electrodes
 Cathode: Reduction
 Anions to Anode
 Anode: Oxidation
Anode:
Cathode:
Geoffrey C. Li
2Br Br2 + 2e
Li+ + e Li(s)
E = 1.07V
E = 3.05V
Product
liquid/gaseous Br2
deposit of Li(s)
Notes by ALog
 51
2Br Br2 + 2e
2H2 O O2(g) + 4H + + 4e
Anode:
E = 0.83V
E = 1.07V
E = 1.23V
2Cl Cl2(g) + 2e
Anode:
2Cl Cl2 + 2e
2H2 O O2(g) + 4H + + 4e
Anode:
E = 0.83V
E = 1.36V
E = 1.23V
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
Anode:
Ag(s) Ag + e
E = 0.83V
E = 1.23V
E = 0.80V
Q: charge (coulomb)
I: current (ampere, C/s)
t: time
n e =
Example: electrolysis of molten CaCl2 between Pt electrodes using 10A current for 5 min
Electrode: Inert Electrolyte: Aqueous
Cathode: Ca2+ + 2e Ca(s)
10 C
1 mol e
1 mol Ca
40.08 g Ca
= 0.623 g
s
96500 C
2 mol e
1 mol Ca
10 C
1 mol e
1 mol Cl2
22.4 L Cl2
= 300 s
= 0.348 L = 348 mL
s
96500 C
2 mol e
1 mol Cl2
WCa = 300 s
VCl2 ,
ST P
19.3 g
cc
= 0.533 g
Au(CN )
4 + 3e Au(s) + 4CN
10
3 mol e
96485 C
1 mol
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 acidbase reaction
H3N: Ag+ :NH3
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)
Conductivity
Geoffrey C. Li
Notes by ALog
 53
[Pt(NH3)6]Cl4
523
[PtCl2(NH3)4]Cl2
228
[PtCl4(NH3)2]
Note: Only Complexes with Coordination Numbers 2, 4 and 6 will be studied for Chem 18
Shapes of Complexes
Coordination Number
Shape
Linear
6
Example: [PtCl5(NH3)] coordination number: 6
Octahedral
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
54 
Chemistry 18: Fundamentals of General Chemistry II
Biological Complexes:
hemoglobin: central atom: Fe
Complex
Primary Valence
Secondary Valence
Denticity
[Ru(NH3)5(H2O)]Cl2
+2
ALL monodentate
[CoBr2(en)2]2SO4
+3
Br: monodentate
en: bidentate
[Fe(CO)5]
ALL monodentate
Mg[Cr(C2O4)2(H2O)2]2
+3
C2O42: bidentate
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)
Geoffrey C. Li
Notes by ALog
 55
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)
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)
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
Co: [Ar]4s23d7
27
Co3+: [Ar]3d6
Co3+ : _ _ _ _ __ __ __ __ __ __ __ __ __
3d
4s
4p
4d
_ _ _ _ __ __ __ +6 e pairs from ligands
3d
4s
4p
4d
_ _ _ _
3d
sp3d2
hybridization to sp3d2
2. Co(CN)63
Co: [Ar]4s23d7
27
Co3+: [Ar]3d6
Co3+ : _ _ _ _ __ __ __ __ __ __ ELECTRON PAIRING
3d
3d
4s
4p
3d
4s
4p
3d
hybridization to d2sp3
d2sp3
 if 3d orbitals are used for coordinate covalent bonds, stronger metalligand bonds are
formed, energy is needed to pair the electrons of the d orbitals
energy released during bond formation > pairing energy
INNER ORBITAL COMPLEX
 enough energy is obtained from bond formation to pair the electrons of the 3d orbitals
energy released during bond formation < pairing energy
OUTER ORBITAL COMPLEX
Tetrahedral
CoCl42
Co2+: [Ar]3d7
Co2+ : _ _ _ __ __ __ __ __ __ __ __ __
3d
4s
4p
4d
Geoffrey C. Li
Notes by ALog
 57
_ _ _
3d
4s
4p
hybridization to sp3
_ _ _
3d
sp3
OUTER ORBITAL COMPLEX
Square Planar
Ni(CN)42
Ni2+: [Ar]3d8
Ni2+ : _ _ __ __ __ __ __ ELECTRON PAIRING
3d
3d
4s
4p
__
3d
4s
4p
3d
hybridization to dsp2
dsp2
58 
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).
= hv =
hc
 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
Weakfield ligands
Strongfield ligands
Examples:
CoF63
(green) Co(CN)63 (yellow)
(toohigh for electrons to reach)
eg
_ _
eg
_ _
t2g
t2g
PARAMAGNETIC (high spin)
 the crystal field theory accounts for the magnetic properties and color of complexes
Square Planar Tetrahedral
__
x2y2
(directly hit)
__
xy
(lobes near ligands)
__ __ __ (t2g)
__
z2
(collar interaction)
__ __ (eg)
__ __
xz yz
Geoffrey C. Li
Notes by ALog
 59
Example:
Ni(CN)2
Ni2+:[Ar]3d8
__
CoCl42
Co2+:[Ar]3d8
_ _ _ (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+: StrongField Ligand: Square Planar
Examples:
1. [Cr(en)3]3+ Cr3+: [Ar]3d3
2. [Mn(CN)6]3 Mn3+:[Ar]3d4
eg
eg
_ _ _
_ _
t
t2g
2g
3.[Co(H2O)6]2+ Co2+:[Ar]3d7
4. [FeCl4]
_ _
eg
_
t2g
Fe3+:[Ar]3d5
_ _ _
t2g
_ _
eg
__
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
60 
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+
Geoffrey C. Li
Notes by ALog
 61