BCHS 3304: General Biochemistry I, Spring 2003 1:00-2:30 PM Mon./Wed. AH 101
BCHS 3304: General Biochemistry I, Spring 2003 1:00-2:30 PM Mon./Wed. AH 101
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=
R = gas constant for a 1M solution
Plot lnKeq vs. 1/T ( remember T is in absolute degrees Kelvin)
lnKeq
R
H -
o
A
= Slope
R
S
o
A
T
1
= Intercept
Vant Hoff plot
K
eq AG
o
(kJmole-1
10
6
-34.3
10
4
-22.8
10
2
-11.4
10
1
-5.7
10
0
0.0
10
-1
5.7
10
-2
11.4
10
-4
22.8
10
-6
34.3
The Variation of K
eq
with AG
o
at 25
o
C
A A = A ) (reactants G - (products) G G
o
f
o
f
o
The f = for formation.
By convention, the free energy of the elements is taken
as zero at 25
o
C
The free energies of any compound can be measured as
a sum of components from the free energies of
formation.
Standard State for Biochemistry
Unit Activity
25
o
C
pH = 7.0 (not 0, as used in chemistry)
[H
2
O] is taken as 1, however, if water is in the Keq equation
then [H
2
O] = 55.5
eq
K
'
o
G
'
A
G
'
A
The prime indicates Biochemical standard state
Most times
o o
G G A =
'
A
However, species with either H
2
O or H
+
requires consideration.
For A + B C + D + nH
2
O
[A][B]
O] [C][D][H
RTln - G
n
2
o
= A
[A][B]
[C][D]
RTln - K RTln - G
eq
o
=
'
=
'
A
This is because water is at unity. Water is 55.5 M
and for 1 mol of H
2
O formed:
O] RTln[H G G
2
o o
n + A =
'
A
-1 o o
mol kJ 9.96 G G - + A =
'
A
For: A + B C + HD
H
+
+ D
-
Where a proton is in the equation
K
[HD]
] ][D [H
K
- +
=
( )
o
o
o o
] H ln[ RT
K
] [H - 1
ln RT - G G
+
+
+ A =
'
A
M 10 ] [H
-7
o
=
+
This is only valid for
Coupled Reactions
A + B C + D AG
1
(1)
D + E F +G AG
2
(2)
0 G
1
> A
If
reaction 1 will not occur as written.
However, if
2
G A
is sufficiently exergonic so
0 G G
2 1
s A + A
Then the combined reactions will be favorable through
the common intermediate D
A + B + E C + F + G AG
3
0 G G G
2 1 3
s A + A = A
As long as the overall pathway is exergonic,
it will operate in a forward manner.
Thus, the free energy of ATP hydrolysis, a
highly exergonic reaction, is harnessed to
drive many otherwise endergonic biological
processes to completion!!
Life obeys the Laws of Thermodynamics
Living organisms are open systems
Living things maintain a steady state
Enzymes catalyze biological reactions
Water and elements in life processes
Lecture 3 1/22/2003