Final Fall 2009 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
F =9.648510
4
Cmol
1
Faraday constant
Formulas
hydrostatic pressure P =gh
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)

r
S

(product)

(reactant)

r
G

f
G

(product)

f
G

(reactant)
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;
ideal solution: a
J
=x
J
; ideal-dilute: solvent a
A
=x
A
and solute a
B
=
[B]
c

r
G =
r
G

+RT lnQ
Q =

i
a

i
i
K =Q
eq
=

i
a

i
i ,eq
equilibrium constant

r
G

=RT lnK; K =exp

_

r
G

RT
_
; ln
_
K
2
K
1
_
=

r
H

R
_
1
T
2

1
T
1
_
log

=A

z
+
z

I , A =0.509; I =
1
2

i
z
2
i
(b
i
/b

)
E
cell
=E =E
R
E
L
(intensive quantity)

r
G =FE;
r
S =F
_
E
T
_
P
;
r
H =F
_
E +T
_
E
T
_
P
_
Final Fall 2009 Physical Chemistry I
E =E

RT
F
lnQ Nernst equation
E

=
RT
F
lnK; E
+
=E

+16.1
RT
F

H
; E
+
=
RT
F
lnK

d[J]
dt
=
J
v
zero order: A
k
P,
d[A]
dt
=k, [A](t ) =[A]
0
kt
rst order: A
k
P,
d[A]
dt
=k[A], ln
_
[A](t )
[A]
0
_
=kt , [A](t ) =[A]
0
exp(kt )
second order: A
k
P,
d[A]
dt
=k[A]
2
, [A](t ) =
[A]
0
1+kt [A]
0
second order: A+B
k
P,
d[A]
dt
=k[A][B],
1
[B]
0
[A]
0
ln
_
[A]
0
[B](t)
[A](t ) [B]
0
_
=kt ;
if [B]
0
=[A]
0
, then
d[A]
dt
=k[A]
2
other orders:(x =1) A
k
P,
d[A]
dt
=k[A]
x
,
1
x 1
_
1
[A](t )
x1

1
[A]
x1
0
_
=kt
half-life: t
1/2
=
ln2
k
=0.693k
1
rst order; t
1/2
=
2
x1
1
(x 1)k[A]
x1
0
(x =1) other orders
k = Aexp
_

E
a
RT
_
relaxation methods: A

B, x(t ) =[A](t ) [A]

eq
=x(0) exp(t /), =
1
k
1
+k
1
, K
c
=k
1
/k
1
Parallel rst-order irreversible reactions:
Y
B
irr
=
[B]()
[A]
0
=
k
1
k
1
+k
2
, Y
C
irr
=
[C]()
[A]
0
=
k
2
k
1
+k
2
, S
irr
=
[B](t )
[C](t )
=
k
1
k
2
Parallel rst-order reversible reactions:
Y
B
rev
=
[B]
eq
[A]
0
=
K
c,1
1+K
c,1
+K
c,2
, Y
C
rev
=
[C]
eq
[A]
0
=
K
c,2
1+K
c,1
+K
c,2
, S
rev
=
[B]
eq
[C]
eq
=
K
c,1
K
c,2
Michaelis-Menten mechanism: E+S
k
1

k
1
(ES)
k
2
P+E,
d[P]
dt
=v =
k
2
[E]
0
[S]
K
M
+[S]
, K
M
=
k
1
+k
2
k
1
,
k
cat
=k
2
=
v
max
[E]
0
, =
k
cat
K
M