CHE102

Clausius-Clapeyron equation
(
)
Hvap 1
1
Pvap1
=

ln
Pvap2
R
T1
T2

Common constant
12.01
19.00
35.45
44.01
100.1

C
F
Cl
CO2
CaCO3
R

NA

N
P
Ag
H2 O
NO2

14.01
30.97
107.9
18.02
46.01

O
S
Pb
HCl
Hg

16.00
32.07
207.2
36.46
200.6

Henrys law
Pi = ki xi

L atm
J
= 0.082058
K mol
K mol
6.02 1023 /mol

mol solute
kg solvent .

Molarity=

Pi
ki

where ki is the Henrys law constant for the solution, xi

is the mole fraction of the gas, and temperature, and Ci
mL gas
is L solvent .
Relationship in liquid phase: k increases, solubility
decreases

8.314

Concentration
Molality=

Ci =

mol solute
L solution .

Daltons
Pi = yi Ptotal
yi : molfraction in vapor

Gases
Kinetic theory
P = 13 m
u2 N
V , where N is the number of molecules.

Raoults
Pi = xi Pivap
xi :mol fraction in liquid

Boiling/freezing point elevation

Van der Waals equation

Tb = iKb m

Tf = iKf m

where i 1 is the van t Ho factor (average # of ions

2
1000g/kg is the
per molecule of solute) and m = m2m/M
1
molality of the solution.

RT
a

=P
Vm b Vm2
)
(
a
P + 2 (Vm b) = RT
Vm

Phase diagram

P Vm3 (bP + RT )Vm2 + aVm ab = 0

where Vm = Vn , a increases with intermolecular attraction, and b increases with gas molecule size.

From lower -> higher T along const. P, enthalpy

increases (heat absorbed)

Compressibility factor

From lower -> higher P along const. T, volume

decreases

Z=

P Vm
RT

Vreal
Videal .

Generally, 0.1 < Z < 1.5.

Osmotic pressure

Eusion and diusion

M2
1
Diusion: Rate
=
Rate2
M1 .

M2
N1
1
Eusion: Rate
Rate2 = N2
M1

= cRT

V = nRT

where c = nV2 is the molar concentration of the solute. n

is the mol of solute

N
Rate of eusion: Zw = 4V
u
A where N is the #
of molecules, V is volume, A is the pinhole area, u
is
Solubility product constant Ksp
average speed.

Ksp = [A]a [B]b

Vapors
Antoines equation

Solubility

B
ln Pvap1 = A
C +T
where A, B, C are constants that depend on the substance and temperature.

(
S=

Ksp
aa bb

1
) a+b

Concentration of solute that can dissolve.

1

Vant Ho Equation
ln

K2
H
=
K1
R

1
1

T1
T2

Galvanic cell

Anode
Cathode
Electrons flow from
to
This happens oxidation reduction
Charge
+
higher E -> better oxidating and the other way
around for reduction. Oxidation: lose e

Percent dissociation
- dont use Vant Ho but this
Tf = Ki mef f

Standard state

Equilibrium

In the standard state, the half-cells have concentrations

of 1.0 M, pressures of 1 atm, and temperatures of 25 C.
If E is positive, the reaction goes .

Equilibrium constant K
For a simple, one-step equilibrium reaction
aA + bB cC + dD

Nernst equation

the equilibrium constant is

For a half-cell reaction

c

K=

[C] [D]
[A]a [B]b

0.0592
RT
o
ln Q
Ecell = Ecell

lnQ
nF
n
where K can be Kc (if [A] is molar concentration of A at
where R = 8.314, n is the # of e transferred, F =
equilibrium) or Kp (if [A] is pressure of A at equilibrium). NA
4
e 9.65 10 is Faradays constant (coulombs per
To convert, Kp = Kc (RT )c+dab . Reverse Kp & Kc by
mole) & Q: reaction quotient. At Ecell = 0, the cell is in
add negative to the exponent
o
equilibrium. For concentration cell, Ecell
=0

Ecell = Ecell

Reaction quotient Q

pH = log10 [H + ]

Use the equilibrium equation with current rather than

equilibrium values. Q = K: reaction is in equilibrium. Relationship b/w K & E
Q < K: reaction goes . Q > K: reaction goes .
9
nEcell
K = 10( 0.0592 )

Electrochemistry
Chemical kinetics

Oxidation states

Rate of reaction r - A, B are reactants, C is product

1 d[A]
1 d[C]
F: 1. Cl, Br, I: 1 except with O or other halogens.
r=
=
= k[A]n [B]m
a dt
c dt
H: +1, but 1 with metals.
Order
Rate law
Integrated Rate
Straight line
Group 1, 2 metals: 1, 2.

O: 2, but 1 for peroxides (H2 O2 ), +2 with F.

Group -1, -2, -3 have corresponding oxidation states.
Balancing redox reactions

0
1
2

R = k[A]
R = k[A]2

Order

R=k

[A]t = kt + [A]o

ln[A]t = kt + ln[A]o
1
1
[A]t = kt + [A]0
Unit

[A] vs time

ln[A] vs time
1
[A] vs time

Half-life

[A]o
0
-ve slope
2k
ln2
1
+ve slope
k
1
2
slope
k[A]o
*** Radioactive is always 1st order
mol
Ls
1
s
L
mols

Write half-reactions.
Balance atoms except H and O.
Balance O by adding H2 O.

Balance H by adding H + to the hydrogen-deficient Arrhenius equation

side (acid) or H2 O to it and OH to the other side
Ea
(base).
k = Ae RT
Balance charges by adding e .

Ea
k2
=
ln
k1
R

1
1

T1
T2

where A is the pre-exponential constant for the reaction

and Ea is the activation energy. Note that you can obtain

Add the two half-reactions to cancel e .

2