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Instructor:
Glen B. Legge, Ph.D., Cambridge UK
Phone: 713-743-8380
Fax: 713-743-2636
E-mail: glegge@uh.edu
Office hours:
Mon. and Wed. (2:30-4:00 PM) or by appointment
353 SR2 (Science and Research Building 2)
Research Interests:
Molecular mechanisms of cell adhesion, using primarily multi-
dimensional nuclear magnetic resonance (NMR) spectroscopy.
Lecture 1 Summary
• Life arose from simple organic molecules
• Compartmentalization gave rise to cells
• All cells are either prokaryotic or eukaryotic
• Eukaryotic cells contain membrane-bound
oragnelles
• Three domains based on phylogeny
– Archea, bacteria, and eukarya
• Natural selection directs evolution
Thermodynamics and chemical
equilibria
• Lecture 2 1/15/2003
• Chapter 1 Voet, Voet and Pratt
Thermodynamics:
Allows a prediction as to the spontaneous nature of
a chemical reaction:
A + B C
If q is negative exothermic
system gives off heat.
H = U + PV
H = U + PV = qp -w + PV = qp - w1
Enthalpy (H)
When considering only pressure/volume work
H = qp - PV + PV = qp
Hot Cold
or
When a driver jumps into the water, energy from that person is
dissipated to the water molecules. Have you ever seen the
water molecules act in unison and retransfer this energy back
to the driver and push him out of the water?
• Disorder increases
• N identical molecules in a
bulb, open the stop cock you
get 2N equally probable
ways that N molecules can
be distributed in the bulb.
But gas molecules are indistinguishable.
N!
WL
L! (N - 1)!
WL
The probability of occurrence of such a state N
(Is its fraction of the total number of states) 2
N = 4 particles, 2 orientations or 24 = 16 different
arrangements of distinguishable particles
1{
4{
6* {
4{
} N+1
different
states
1{
* The most probable state is the one with the most arrangements
The state that is the most probable is one with the highest
value of WL= N/2 in one bulb and N/2 in the other.
For N=10 the probability that L lies within 20% of N/2 = .66
N=50 probability L lies within 20% of N/2 = .88
N=1023 , L = 1
10-434 = 0
The reason that direction occurs is not by the laws of
motion, but the aggregate probability of all other states is
So low!! or insignificant that only the most probable state
will occur.
Entropy
WN 10 NLn2
Possible arrangements
S k b LnW
Each molecule has an inherent amount of energy which
drives it to the most probable state or maximum disorder.
This means if no energy flows into the bulbs from the outside
expansion will cool the gas! Conservation of Energy says that
the increase in Entropy is the same as the decrease in thermal
(kinetic) energy of the molecules!!
Entropy is the arrow of time
G = H - TS
Describes the total usable energy of a system
G = H - TS = qp - TS
- - Enthalpy favored.
Spontaneous at
temperature below
T = H
S
+ + Entropy driven,
enthalpy opposed.
Spontaneous at
Temperatures above
T = H
S
- + Non-spontaneous
STP
Standard Temperature and Pressure and at 1M concentration.
aA + bB cC + dD
[A]a [B] b
Now if we are at equilibrium or G = 0
Then
c d
[C] [D]
G 0 G RTln
o
a b
[A] [B]
c d
[C] [D]
G RTln
o
[A]a [B] b
OR
G RTlnK eq
o
Go
Keq
If Keq = 1 then G = 0
However
The initial products and reactants maybe far from their equilibrium
concentrations
c d
so
[C] [D] Must be used
a b
[A] [B]
c d G o
[C] [D]
Keq e
eq eq RT
a b
[A] [B]
eq eq
Le Chatelier’s principle
Any deviation from equilibrium stimulates a process which restores
equilibrium. All closed systems must therefore reach equilibrium
What does this mean?
Keq varies with 1/T
If Keq varied with temperature things would be very unstable.
Exothermic reactions would heat up causing an increase in Keq
generating more heat etc….
Fortunately, this does not happen in nature.
- H 1 S
o o
lnK eq
R T R
R = gas constant for a 1M solution
Plot lnKeq vs. 1/T ( remember T is in absolute degrees Kelvin)
Van’t Hoff plot
- H o
lnKeq = Slope
R
So = Intercept
R
1
T
The Variation of Keq with Go at 25 oC
Keq o
G
(kJ·mole-1
106 -34.3
104 -22.8
102 -11.4
101 -5.7
100 0.0
10-1 5.7
10-2 11.4
10-4 22.8
10-6 34.3
G G (products) - G (reactants )
o o
f
o
f
Unit Activity
25 oC
pH = 7.0 (not 0, as used in chemistry)
[H2O] is taken as 1, however, if water is in the Keq equation
then [H2O] = 55.5
K eq G o
G
Most times G G o o
For A + B C + D + nH2O
n
[C][D][H O] [C][D]
G o - RTln 2
G - RTln Keq - RTln
o
[A][B] [A][B]
This is because water is at unity. Water is 55.5 M
and for 1 mol of H2O formed:
H+ + D - -
[H ][D ]
Where a proton is in the equation K
[HD]
Go G o - RT ln
1 - [H ]
RT ln[ H
o
]o
K
This is only valid for [H ]o 10 M -7
Coupled Reactions
• Lecture 3 1/22/2003