Test 3 Fall 2010 Physical Chemistry I

Constants
g =9.81ms
2
gravitational acceleration
N
A
=6.02210
23
mol
1
Avogadro constant
R =8.314J mol
1
K
1
=0.08206Latmmol
1
K
1
gas constant
1atm760Torr =760mmHg 1.0132510
5
Pa
1bar 10
5
Pa
Formulas
hydrostatic pressure P =gh
phase equilibrium:
trs
S =

trs
H
T
trs
G H TS =U +PV TS; dG =V dP SdT
T =const : G =V (P
2
P
1
) (solids or liquids), G =nRT ln
_
P
2
P
1
_
(ideal gas)
phase boundary:
dP
dT
=
S
V
=
H
TV
Clapeyron equation
solid-gas or liquid-gas boundary:
dlnP
dT
=
H
RT
2
Clausius-Clapeyron equation
vapor pressure: ln
_
P
2
P
1
_
=
H
R
_
1
T
2

1
T
1
_
, P
2
=P
1
exp
_

H
R
_
1
T
2

1
T
1
_
_
solid-liquid boundary: P
2
=P
1
+
H
fus
V
fus
ln
_
T
2
T
1
_
P
1
+
H
fus
T
1
V
fus

_
T
2
T
1
_
Troutons rule: S
vap
85J K
1
mol
1
V =
N

i =1
n
i
V
i
T =const, P =const
G =
N

i =1

i
n
i
Daltons law: P =

J
P
J
; P
J
=
n
J
RT
V
; P
J
=x
J
P
x
J
=b
J
M
solv
; c
J
=b
J

solv
; M
solv
in kg/mol;
solv
in kg/L

J
(T, P) =

J
+RT lna
J
; ideal gas: a
J
=
P
J
P

; pure solid or liquid: a

J
=1;
Test 3 Fall 2010 Physical Chemistry I
ideal solution: a
J
=x
J
; ideal-dilute: solvent a
A
=x
A
and solute a
B
=
[B]
c

or a
B
=
b
b

Raoults law: P
A
=x
A
P

A
; Henrys law: P
B
=x
B
K
B
mixing, ideal solutions (T =const, P =const):
mix
G =nRT
_
x
A
lnx
A
+x
B
lnx
B
_
,

mix
S =nR
_
x
A
lnx
A
+x
B
lnx
B
_
,
mix
H =
mix
U =
mix
V =0
Convention I: a
i
=
P
i
P

i
=
i
x
i
for all i
Convention II: a
A
=
P
A
P

A
=
A
x
A
; a
B
=
P
B
K
B
=
B
x
B
A=solvent, B=solute
or using molarity or molality for B: a
B
=
B
c
B
c

or a
B
=
B
b
B
b

; c

=1mol/L, b

=1mol/kg
log

=A

z
+
z

I , A =0.509, I =
1
2

i
z
2
i
(b
i
/b

)
colligative properties:
lna
A
=
H
A,vap
R
_
1
T
b

1
T

b
_
, T
b
=T
b
T

b
=
RT
2
b
H
A,vap
x
B
=K
b,x
x
B
=K
b
b
B
lna
A
=
H
A,frz
R
_
1
T
f

1
T

f
_
, T
f
=T

f
T
f
=
RT
2
f
H
A,fus
x
B
=K
f,x
x
B
=K
f
b
B
lna
A
=
V

A
RT

vant Hoff equation: =

n
B
V
RT =c
B
RT =[B]RT
ideal solubility: lnx
B
=
H
B,fus
R
_
1
T

f ,B

1
T
_