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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
f  (x) = nxn1

2. f (x) = xn

f  (x) = 3(4)x31 = 12x2

Example: f (x) = 4x3


3. d(u + v) = du + dv

Example: f (x) = 3x2 2x + 4


f  (x) = 6x 2
10
4
y  = 5 + 4x2 20x3
Example: y = 5x 3 + 2
x x
= 5x 3 4x1 + 10x2
4. d(uv) = udv + vdu or 1d2, 2d1
f  (x) = (3x 5)(8x) + (4x2 3)(3)

Example: f (x) = (3x 5)(4x2 3)


 u  vdu udv

ldh hdl
v
l2
2
4x + 3x 5
Example: f (x) =
2x + 1

5. d

v2

or

f  (x) =

(2x + 1)(8x + 3) (4x2 + 3x 5)(2)


(2x + 1)2

6. Chain Rule
f  (x) = 2(4x2 7x + 13)(8x 7)

Example: f (x) = (4x2 7x + 13)2

Integration: finding the area under the curve

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
ln|x| + 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 10ln|v| +
1
= 5v 10ln|v| 12v 1 + C

Geoffrey C. Li

Notes by A-Log

| 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 4ln|t| + 10
2
1 t
2t

7
= t2 3t 4ln|t| 10t1 
2
t



7
2
2
(2t) t 3 (2t t) 4 (ln|2t| ln|t|) 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 |

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
ranges from -1 to 1, -1/1 means a straight line
y = the value of y when x is...
Example: 20
y

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

[B] is changing at the greatest rate

For the reaction: 3X + 5Y 2Z


Rate of reaction =

1 d[X]
1 d[Y ]
1 d[Z]
=
=
2 dt
3 dt
5 dt

[Y] is changing at the greatest rate

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 +

[N O2 ] is changing at the greatest rate

Geoffrey C. Li

Notes by A-Log

| 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

Given: 4N H3(g) + 5O2(g) 4N O(g) + 6H2 O(g)

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:

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


k


rate constant

p


steric factor (orientation)

Z


frequency of collision

Ea

RT
e  

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
4 |

Chemistry 18: Fundamentals of General Chemistry II

- 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;
- more molecules are available for collision

Rate [reactants]n

Rate Law:

k = rate constant
rate = k[reactants] n = order of reaction
n

- 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]
0.010 M
0.010 M
0.020 M

[B]
0.010 M
0.020 M
0.010 M

Initial Rate (M/s)


1.2 104
2.4 104
4.9 104

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

Overall Order: 2+1=3


rate
[A]2 [B]
1.2 104
=
(0.010M )2 (0.01M )

Substitute Experiment 1: k =

= 120 M 2 s1

Double A? 4 Rate

Double B? 2 Rate

[2A] [2B]? 8 Rate

Rate = (120 M 2 s1 )[A]2 [B]

[0.5A]2 [2B]? 0.5 Rate

[2A]2 [0.5B]? 2 Rate

b. Differential Method
Rate = k[A]n

Plot log Rate vs log [A]

log Rate = log k + n log[A]


        
y

Geoffrey C. Li

mx

slope = n
y-int = logk

Notes by A-Log

| 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

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

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

mx

Plot log rate vs log [C]


slope = z
y-int = log k[A]x [B]y


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]

Plot log rate vs log [A]


r = 0.99999
B = 0.996 1 = x
A = 2.032 = log k[B]y

Plot log rate vs log [B]


r = 0.999998
B = 1.99 2 = 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(0.020) = 0.67912

log k(0.030)2 = 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

Chemistry 18: Fundamentals of General Chemistry II

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

Initial Rate (M/s)


3.20 105
2.90 104
1.15 103
4.61 103
1.40 104
7.25 105
3.71 105

rate = k[HgCl2 ]x [C2 O42 ]y


[C2 O2
4 ]: at constant [HgCl2 ]
x

log rate = log k[HgCl2 ] +

[HgCl2 ]: at constant [C2 O2


4 ]

y log[C2 O42 ]

Plot log rate vs log [C2 O2


4 ]
r = 0.9999
slope = y = 1.99 2

log rate = log k[C2 O42 ]y + x log[HgCl2 ]


Plot log rate vs log [HgCl2 ]
r = 0.9999
slope = y = 0.995 1

rate = k[HgCl2 ][C2 O42 ]2


When [HgCl2 ] = 0.12 M and [C2 O2
4 ] = 0.10 M:

From constant [C2 O2


4 ]:
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

2.76213 = log k(0.45)2


3

k = 8.54 10

rate = 1.02 105 M/s

2 1

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]
= 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 [A]0 = k(t 0)


[A]t = kt + [A]0
  

[A]t

t
1
[A] d[A] = k dt

mx

[A]0

Plot [A] vs t
slope = -k
y-int = [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
y-int = ln[A]0

Geoffrey C. Li

Notes by A-Log

| 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
y-int =

[A]0

1
vs t
2[A]2
slope = k
1
y-int =
2[A]20

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
= kt +
n=3:
2
2[A]t
2[A]20
Example:
Given: 2C5 H6 C10 H12

[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

The reaction is a second-order reaction.

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=

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


1
x
= 612 s
t=
(0.20)(0.0400)

Half-Life t1/2
- time required to reduce the concentration of the reactant to half of its initial value
8 |

Chemistry 18: Fundamentals of General Chemistry II

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

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

t 12 =

ln 2
k

ln 2
= 0.0578 min1
12.0 min

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


ln

(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 A-Log

| 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. half-life 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

Gas-Phase Reactions

A(g) B(g) + 2C(g)

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

from PV = nRT, P = MRT, C =

P
RT

Therefore,

ln

PA,t
RT
PA,0
RT

ln

PA,t
= kt
PA,0

= kt

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
= 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

min1 )(600 min)

)(800 mmHg) = 4.43 mmHg

Chemistry 18: Fundamentals of General Chemistry II

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

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

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

T: absolute tempterature (in K)


A: pre-exponential factor

1
T

Ea
slope =
R
y-int = 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 half-life 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 A-Log

| 11

Quiz
Given: n=2
Ea = 250 kJ/mol

[N2 O]t = 0.20[N2 O]0 = 0.002 M

T1 = 838.15 K

t 12 = 25.25 hours

T2 = 973.15 K

t =?

[N2 O]0 = 0.01 M

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

Overall Reaction: 2H2 O2 2H2 O + O2


H2 O2 + I H2 O + OI
H2 O2 + OI H2 O + O2 + I
2H2 O2 2H2 O + O2

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 one transition state for each step

Has no intermediate

Has one or more intermediates


same change in enthalpy

12 |

Chemistry 18: Fundamentals of General Chemistry II

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
k

NO2 + NO2

k2

CO + NO3
CO + NO2

Rate = k [NO2 ]2

NO3 + NO

(slow)

CO2 + NO2
CO2 + NO

(fast)

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
NO + Cl2
NO + NOCl2
2NO + Cl2

k2

NOCl2

(slow)

2NOCl
2NOCl

(fast)

Step 1 is the rate determining step: Rate = k1 [N O][Cl2 ]


The proposed mechanism is not plausible

Geoffrey C. Li

Notes by A-Log

| 13

Mechanism 2
NO + Cl2
NO + NOCl2
2NO + Cl2

NOCl2
2NOCl
2NOCl

(fast)
(slow)

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
K=

[N OCl2 ]
[N O][Cl2 ]

[N OCl2 ] = K[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])
[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

Rate = k[A]2 [B]

A+A
A2 + B
AB + B
A + 2B

A2
AB + A
C
C

(fast)
(slow)
(fast)

Rate = k2 [A2 ][B]

14 |

Chemistry 18: Fundamentals of General Chemistry II

Equilibrium Method:
K=

[A2 ]
[A]2

[A2 ] = K[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])
[A2 ] =

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 =

If k2 >>> k1 k1 + k2 [B] k2 [B]

k2 k1 [A]2 [B]
= k1 [A]2
k2 [B]
Does not hold with experimental rate law
This means that rate2 < rate1
Rate =

Chain Reaction / Mechanism



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

H2 + Br2 2HBr

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 A-Log

| 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 ]

Rate = k2 K[I ][OCl ][OH ]1


Rate = k[I ][OCl ][OH ]1
Steady State Approximation
k1 [OCl ] = k1 [HOCl][OH ] + k2 [I ][HOCl]
Rate =

[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

Change that occurs

formation/breaking of bonds

transformation of the nucleus 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: mass #: p + n (nucleons)
A
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

16 |

Chemistry 18: Fundamentals of General Chemistry II

proton: 11 p or 11 H

electron:

0
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


0
0
Beta Particle: 1 e or 1

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

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
Example: 15 P 14 Si +1 e

10 n +01 e

e. Electron capture: done by nuclei with low n/p ratio



p, n, n\p ratio

40
0
40
Example: 19 K +1 e 18 Ar

1
1p

1
1p

+01 e 10 n

Radioactive Disintegration Series


- after one instance of decay, a nucleus can still undergo decay

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 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
k
0

Geoffrey C. Li

Notes by A-Log

| 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)

(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
atomic mass = 27.96924
14 Si

atomic mass = 14 protons

1.00728 amu
proton

+ 14 neutrons

1.00867 amu
neutron

m = calculated mass - actual mass = 28.22330 amu 27.96294 amu


m = 0.25406 amu
E = mc2

= 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

E = (0.25406 amu)(3 108 )2

18 |

Chemistry 18: Fundamentals of General Chemistry II

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

atomic mass = 55.92066

atomic mass = 26 protons

1.00728 amu
proton

+ 30 neutrons

1.00867 amu
neutron

m = calculated mass - actual mass = 56.44938 amu 55.92066 amu


m = 0.52872 amu
E = mc2

= 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

E = (0.52872 amu)(3 108 )2

2. Nuclear Transmutation: bombardment of a nucleus by a particle to form another nucleus


Examples:

14
7 N

1
+42 He 17
8 O +1 H

9
4 Be

1
+42 He 12
6 C +0 n

bombarded (bombarder, new particle) new nucleus


Short-Hand:
14
17
9
12
4 Be (, n) 6 C

Example: 7 N (, p) 8 O

Transuranium Elements

- man-made 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

3. Nuclear Fission: splitting of a heavy nucleus to form two lighter nuclei


235
92 U

+10 n

142
56 Ba

1
+91
36 Kr + 30 n

Nuclear Chain Reaction


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

Geoffrey C. Li

Notes by A-Log

| 19

- 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

H2 O+ + H2 O H3 O+ + OH

OH starts a chain reaction that affects cells

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

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



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
20 |

Chemistry 18: Fundamentals of General Chemistry II

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

Intensive Property =

Extensive Property 1
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
(+) w = work is done on the system

(-) q
(-) w

= heat is released by the system


= work is done by the system

Note, in Chemistry, work is defined as the Pressure-Volume work (compression/expansion)


Heat, q

(+) q
(-) q

q = mcT

= heat is absorbed by the system


= heat is released by the system

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 A-Log

| 21

Work, w

(+) w = work is done on the system


(-) w = work is done by the system
P-V work: P =

w = F dx




F
A

F = PA
A dx = dV

A: cross-sectional area
P: external pressure

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

w = P dV

P dV

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

Two Types of Work


Irreversible Work - actual work that we do

wirrev =

Pext dV


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

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

2. Isocoric (Constant Volume)

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 A-Log

| 23

For Isobaric Systems, qP is called H

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

For Ideal Gases: 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

B: against a constant pressure of 2 atm (irreversible)


H = 0
wirrev =

U = 0 (isothermal system)
V2

Pext dV = Pext

V1

V2

dV

V1

wirrev = Pext (V2 V1 )


wirrev = (2atm)(4L 2L)
wirrev = 4 Latm
q = w
q = 405.26 J

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

Chemistry 18: Fundamentals of General Chemistry II

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 A-Log

| 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

(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) )


Bomb Calorimeter

m = 1.800 g
T1 = 21.36 C

Ccal = 11.66 kJ/ C


T2 = 26.37 C

qtotal = 0
qcombustion + qcal = 0
qcombustion = qcal = Ccal T

qcombustion = qV = 58.42 kJ per 1.8 g phenol




94.12 g
58.42 kJ
1.8 g
1 mol
kJ
U = 3054.72
mol

U =

H = U + ng RT
average temp: 298.15 K

C6 H5 OH(s) + 7O2(g) 6CO2(g) + 3H2 O(l)


ng = 6 7 = 1




kJ
J
1 kJ
+ (1) 8.314
(298.15 K)
mol
molK
1000 J
kJ
H = 3057.20
mol
H = 3054.72

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)

26 |

Chemistry 18: Fundamentals of General Chemistry II

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)

= 0 (is not a gas in standard state; liquid)

Hf,

Cgraphite

Hf,

Cdiamond

= 0 (stable allotrope in standard state)


= 0

Hrxn = nHf , products nHf , reactants


Example

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

3. Hess' Law of Heat Summation


- possible because H is a state function

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 A-Log

| 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 =

3[N2 O(g) + H2(g) N 2(g) + H2 O(g) ]


1
3[H2(g) + O2(g) H2 O(l) ]
2

Overall : 2N H3(g) + 3N2 O(g) 4N 2(g) + 3H2 O(l)


kJ
kJ
kJ
367.4
285.9
HT = 1531
= 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:
C4 H10(g) +

13
O2(g) 4CO2(g) + 5H2 O(g)
2

Using Standard Heats of Formation:


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
= 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
+ (10 mol) 463
(8 mol) 799
mol
mol
= 2630.5kJ

C4 H10(g) + 13
2 O2(g)
5H2 O(g)
C4 H10(g) + 13
2 O2(g)

4CO2(g) + 5H2 O(g)


5H2 O(l)
4CO2(g) + 5H2 O(l)

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

Ccal = 7.62 kJ/ C


Bomb Calorimeter

Chemistry 18: Fundamentals of General Chemistry II

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) +

Hrxn = nHf , products nHf , reactants







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





kJ
13

mol) 0
(1 mol) Hf, C8 H18 + (
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

dS =

dqrev
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

Geoffrey C. Li

Notes by A-Log

| 29

Ideal Gas System


1. Isobaric 2. Isocoric

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

Phase Changes (constant T and constant P)

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

Hf us, ice = 6.02 kJ/mol


ice CP = 37.7 J/molK

Tf = 383.15 K
Hvap,

water

Ti = 268.15 K

= 40.67 kJ/mol

liquid water CP = 75.3 J/molK


steam CP = 33.9 J/molK


30 |


 

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

Chemistry 18: Fundamentals of General Chemistry II

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

Svap = 86.9 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

Alternative Basis for Spontaneity

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: Gibb's Free Energy


- available energy needed to do useful work

G=

H


heat available

Geoffrey C. Li


TS

heat used

G = H T S
Notes by A-Log

| 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

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

32 |

Chemistry 18: Fundamentals of General Chemistry II



kJ
q = nHvap = (2 mol) 40.67
= 81.34 kJ
mol

w = (reversible, since slow process)


= Pext

V2

dV = Pext (V2 V1 )

V1

= Pext (Vgas Vliq )

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

= 81.34 kJ 6.205 kJ = 75.135 kJ


H = qP = 81.34 kJ


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


kJ
=0
G = H T S = 81.34 kJ (373.15 K) 0.218
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
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 A-Log

| 33

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
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

(thermodynamic/true equilibrium constant)

aN O2

Ka =

G
RT

aN2 2 aO2

activity = true pressure = P


= activity coefficient (correction factor to account for non-ideal pressure
Ka =

PN O2
1
2

N O2
1
2

N2 O2

(PN2 ) PO2
Ka = K KP

If gases are ideal, = 1, a = P


PN O 2
Ka KP =
1
PN2 2 PO2

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

Chemistry 18: Fundamentals of General Chemistry II

Grxn = nGf,p nGf,r


kJ
1 mol (0 + 0) = 51.84 kJ
= 51.84
mol
K a = e
=e

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

2N O(g)  N2(g) + O2(g)


3
3N O(g) + Br2(g)  3N OBr(g)
2

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

= (8.314 103 kJ/molK)(298.15 K)(ln 8.944 105 ) = 91.05

kJ
mol

Molecular Equilibrium
Solving Equilibrium Problems

1. Write the balanced equilibrium equation
Geoffrey C. Li

Notes by A-Log

| 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

12.5% decomposed at equilibrium

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
300-x

+ O2(g)

PCl = 250 mmHg




-(0.5)x
250-0.5x

Peq = 420 mmHg

T = 473.15 K

NOCl(g)
0M
+x
x

300 x + 250 0.5x + x = 420


x = 260
N O : 40mmHg
Cl2 : 120mmHg
N OCl : 260mmHg

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

3. Given: Initial: 0.40 mol NH3


2NH3 
I (mol)
0.4
C (mol)
-0.1
E (mol)
0.30
mT OT AL = 0.5 mol

36 |

N2
0
+0.05
0.05

Equilibrium: 0.15 mol H2 at 2 atm


+

3H2
0
+0.15
0.15

Chemistry 18: Fundamentals of General Chemistry II

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 =

4. Given: Initial: 0.125 mol COCl2 in 2.00L


COCl2(g)
0.125 M
-x
0.125 - x M

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

Equilibrium: 0.0400 mol NO2

[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

KP (for ideal gases, = 1) = PN H3 PHCl

KC = [N H3 ][HCl]

F e(s) + H2 O(l)  F eO(s) + H2(g)


2Ag(s) + 12 O2(g)  Ag2 O(s)

KC =
KP =

C(s) + CO2(g)  2CO(g)

KC =

[H2 ]
[H2 O]
1
0.5
PO
2
[CO]2
[CO2 ]

1. Given: PT = 450 mmHg at 298.15 K


I
C
E

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 A-Log

| 37

KC = 1.2 104 at 303.15 K

2. Given: 2.5 mol NH4 HS in 2L


I
C
E

NH4 HS(s)
-

NH3(g)
0
+y
y

At Equilibrium: [NH3 ]=0.011 M

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

3. Given: 0.30 mol CCl4 , 0.010 mol Cl2 in 2L


I
C
E

CCl4(g)
0.15 M
-z
0.15 - z

C(s)
-

2Cl2(g)
0.005 M
+ 2z
0.005 + 2z

At Equilibrium: [CCl4 ] = 0.1317 M

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

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


Addition of B: shift to the RIGHT
Addition of P: shift to the LEFT

2. Pressure/Volume (for gases)


P (resulting in V) shift to the RIGHT
P, shift to the lesser number of moles)

Removal of A: shift to the LEFT


Removal of B: shift to the LEFT
Removal of P: shift to the RIGHT

P (resulting in V) shift to the LEFT


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 favors endothermic processes
H>0 (heat in the reactants)

T shift to the RIGHT


T favors exothermic processes
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

G = RT ln K + RT ln Q
Q
G = RT ln
K
38 |

Q < K, G < 0, forward shift


Q = K, G = 0, equilibrium
Q > K, G > 0, backward shift

Chemistry 18: Fundamentals of General Chemistry II

Example: Given: 0.5 M COCl2 in 2L


I
C
E

COCl2(g)
0.5 M
-a
0.5 - a

CO(g)
0
+a
a

KC = 8

Cl2(g)
0
+a
a

At Equilibrium: [COCl2 ] = 0.028 M

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

At New Equilibrium: [COCl2 ] = 0.0529 M

[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
y-int:
R

Plot lnKa vs

Two-point form:

ln

H
Ka2
=
Ka1
R

1
1

T2
T1

Exothermic: +

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


Geoffrey C. Li

Notes by A-Log

| 39

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
+
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

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
40 |

Chemistry 18: Fundamentals of General Chemistry II

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- > FIonization 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


pH < 7

pH + pOH = pKw
at 298.15 K, pH + pOH = 14

pOH > 7

N eutral : [H3 O ] = [OH ] = 1.0 107


pH = pOH = 7
+

[OH ] < 1.0 107

Base : [H3 O+ ] < 1.0 107


pH > 7

[OH ] > 1.0 107

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 A-Log

| 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 - acid ionization/dissociation constant

Ka =

[H3 O+ ][A ]
[HA]

Examples: HF, organic acids (R-COOH)

B(aq) + H2 O(l)  BH(aq)


+ OH(aq)

Kb - base ionization/dissociation constant

Kb =

[BH + ][OH ]
[B]

Examples: organic bases (R-NH2 )

Polyprotic Acids
+

H3 P O4(aq) + H2 O(l)  H3 O(aq)


+ H2 P O4(aq)
2

+
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)

Ka1 = 7.5 103


Ka2 = 6.2 108
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
+

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)

Salts of Weak Acids and Strong Bases


N aF(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

Salts of Strong Acids and Weak Bases


N H4 Cl(aq)

+
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 |

Chemistry 18: Fundamentals of General Chemistry II

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

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 =

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)
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
+

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


+ HCO3(aq)

+
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)

Ka2 = 5.6 1011


KW
Kb = K
= 2.33 108
a1

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)
2

+
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)

Ka1 = 7.5 103


Ka2 = 6.2 108
Ka3 = 4.2 1013

Find out if Na3PO4, Na2HPO4 and NaH2PO4 are basic or acidic.


Common Ion Effect
Geoffrey C. Li

Notes by A-Log

| 43

- 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)

Ka =

[H3 O+ ][A ]
[HA]

[A ]
[HA]
[A ]
log[H3 O+ ] = log Ka + log
[HA]

log Ka = log[H3 O+ ] + log

pH = pKa + log

[A ]
(Henderson-Hasselbalch Equation)
[HA]

pOH = pKb + log

[BH + ]
[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.
[In ]
[HIn]

[HIn]
[In ]

10

base color predominates

10

acid color predominates

pH range
+1
pKa
-1

- pH ranges are dependent on pKa



Examples: phenolphthalein, bromthymol blue
44 |

Chemistry 18: Fundamentals of General Chemistry II

Acid-Base Titration
- technique used to determine the concentration of an acid or base, using a known concentration 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
2+
Cu2+
(aq) + 4N H3(aq)  Cu(N H3 )4(aq)

+
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)

KSP = [Al3+ ][OH ]3 = 1.8 1033

- 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

Geoffrey C. Li

Notes by A-Log

| 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)

Ksp = [P b2+ ][I ]2

Qsp = [P b2+ ]0 [I ]20 Q: ion product


Q < Ksp
Q = Ksp
Q > Ksp

no precipitate (unsaturated solution)


maximum amount dissolved (saturated solution)
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
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

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
+
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 reduction-oxidation reactions
46 |

Chemistry 18: Fundamentals of General Chemistry II

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)



Geoffrey C. Li

+
2H(aq)
+ 2e H2(g)

E = 0V

- electrode potential arbitrarily assigned as 0


- used platinum (an inert electrode, doesnt react) as the solid electrode
Notes by A-Log

| 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

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- > 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. Zn|Zn2+ ||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. Ag|Ag + ||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

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:
Cathode:
Cell Reaction:

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

Ecell > 0, Galvanic

Thermodynamics of Electrochemical Cells


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

E: electrode potential
48 |

Chemistry 18: Fundamentals of General Chemistry II

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
ln Q
nF

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)

Determine the potential of the following cells:


1. P b|P b2+ (0.010M )||Co3+ (0.050M ), Co2+ (0.0040M )|P t
[P b2+ + 2e P b(s)]
2[Co3+ + e Co2+ ]
P b(s) + 2Co3+ P b2+ + 2Co2+

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

2. Cu|Cu2+ (0.50M )||Cr2 O72 (0.060M ), H + (0.0040M ), Cr3+ (0.080M )|P t


3[Cu2+ + 2e Cu(s)]
+ 14H + + 6e 2Cr3+ + 7H2 O
3Cu(s) + Cr2 O72 + 14H + 3Cu2+ + 2Cr3+ + 7H2 O

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

Ecell = Ecathode Eanode = 1.82V (0.13V ) = 1.95V


nE

K = 10 0.0592 = 10

Geoffrey C. Li

21.95V
0.0592

= 7.56 1065

Notes by A-Log

| 49

2. M g(s) + 2HCl(aq) M gCl2(aq) + H2(g)


Anode:
Cathode:
Cell Reaction:
nE

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

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:
Cathode:
Cell Reaction:
nE

[Ag + + e Ag(s)]

AgCl(s) + e Ag(s) + Cl(aq)


+

AgCl(s)  Ag(aq) + Cl(aq)

Ksp = 10 0.0592 = 10

10.58V
0.0592

E = 0.80V
E = 0.22V

Ecell
= 0.58V

= 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:
Cathode:
Cell Reaction:

5[F e3+ + e F e2+ ]

M nO4 + 8H + 5e M n2 + 4H2 O]

M nO4 + 8H + + 5F e2+ M n2 + 4H2 O +

5F e3+

E = 0.77V
E = 1.51V

Ecell
= 0.74V

[M n2+ ][F e3+ ]5


0.0592
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
< 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, 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
50 |

Chemistry 18: Fundamentals of General Chemistry II


- 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

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

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 A-Log

| 51

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)

2Br Br2 + 2e
2H2 O O2(g) + 4H + + 4e

Anode:

E = 0.83V
E = 1.07V
E = 1.23V

3. Electrolysis of molten NaCl between Pt electrodes


Electrode: Inert Electrolyte: Molten
Cathode: N a+ + e N a(s)

2Cl Cl2(g) + 2e

Anode:

4. Electrolysis of aqueous NaCl between Pt electrodes


Electrode: Inert Electrolyte: Aqueous
Cathode:
N a+ + e N a(s)
E = 2.71V

2H2 O + 2e H2(g) + 2OH(aq)

2Cl Cl2 + 2e
2H2 O O2(g) + 4H + + 4e

Anode:

E = 0.83V
E = 1.36V
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
Anode:

2H2 O + 2e H2(g) + 2OH(aq)

XN O3 most oxidized form of N


2H2 O O2(g) + 4H + + 4e
+

Ag(s) Ag + e

E = 0.83V
E = 1.23V
E = 0.80V

if Oxidation State = Valence electrons, it is the most oxidized form

Faraday's Law of Electrolysis


- products formed n current
Q = It

Q: charge (coulomb)
I: current (ampere, C/s)
t: time

n e =

Q n: moles of electrons (Faraday)


F F: Faradays constant (96485 or 96500 C/mol e-)

Example: electrolysis of molten CaCl2 between Pt electrodes using 10A current for 5 min
Electrode: Inert Electrolyte: Aqueous

Cathode: Ca2+ + 2e Ca(s)

Anode: 2Cl Cl2(g) + 2e


52 |

Chemistry 18: Fundamentals of General Chemistry II





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

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


WAu = 0.0276 cc

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 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
Geoffrey C. Li

Notes by A-Log

| 53

- 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]

Note: Only Complexes with Coordination Numbers 2, 4 and 6 will be studied for Chem 18
Shapes of Complexes

Coordination Number

Shape

Linear

Tetrahedral or Square Planar

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

ligands: heme, globin, oxygen

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 A-Log

| 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)

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


56 |

- measures optical activity


- creates plane polarized light and shows how a solution of
enantiomers rotate it
Chemistry 18: Fundamentals of General Chemistry II

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

OUTER ORBITAL COMPLEX

2. Co(CN)63-
Co: [Ar]4s23d7
27
Co3+: [Ar]3d6
Co3+ : _ _ _ _ __ __ __ __ __ __ ELECTRON PAIRING

3d
3d
4s
4p



3d
4s
4p

+6 e- pairs from ligands



3d

hybridization to d2sp3


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
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 A-Log

| 57

_ _ _

3d
4s
4p

+4 e- pairs from ligands

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

+4 e- pairs from ligands



3d

hybridization to dsp2


dsp2

INNER ORBITAL COMPLEX

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 orbitals 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

58 |

Chemistry 18: Fundamentals of General Chemistry II

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 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)

__

xy
(lobes near ligands)

__ __ __ (t2g)


__
z2
(collar interaction)

__ __ (eg)

__ __
xz yz

Geoffrey C. Li

Notes by A-Log

| 59

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
Examples:
1. [Cr(en)3]3+ Cr3+: [Ar]3d3

Weak Field Ligand: Tetrahedral

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

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

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Chemistry 18: Fundamentals of General Chemistry II

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

Geoffrey C. Li

Notes by A-Log

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