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Lecture 1: Thermodynamics: CHEM 452: Physical Chemistry For Biochemists

Thermodynamics describes the macroscopic properties of equilibrium systems using four laws. It involves accounting for energy and matter exchanges between a system and its surroundings to predict reactions and phase changes. The zeroth law defines temperature, while the first law defines energy and establishes the principle of conservation of energy. Ideal gas laws describe the behavior of gases using state variables like pressure, volume, and temperature. Real gases are better described by equations of state like the van der Waals equation.

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62 views

Lecture 1: Thermodynamics: CHEM 452: Physical Chemistry For Biochemists

Thermodynamics describes the macroscopic properties of equilibrium systems using four laws. It involves accounting for energy and matter exchanges between a system and its surroundings to predict reactions and phase changes. The zeroth law defines temperature, while the first law defines energy and establishes the principle of conservation of energy. Ideal gas laws describe the behavior of gases using state variables like pressure, volume, and temperature. Real gases are better described by equations of state like the van der Waals equation.

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moien
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© © All Rights Reserved
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Lecture 1: Thermodynamics

CHEM 452: Physical Chemistry for Biochemists


The proper study of biology should really begin with the
theme of energy and its transformations.
- Biochemistry by Albert L. Lehninger

What is a chemical (or physical) system


How to keep track of all the particles (system and
surroundings)
Ideal and real gasses
Thermodynamics and the Greek view of the natural
world
Working problems.

A very brief review of Chemistry 152; Chapters 9 and 10 of


Zumdahl; The 4 laws of Thermodynamics
Basic Physical ideas of energy:
K .E. = 12 mv 2

U = EIMG = 32 PV

P.E.gr = mgh

E = cp = h Photon

P.E.Coul

Ze 2
=
r

c =

Work and heat transfer; system/surroundings; State Fns.


PV = nRT
w = F h = Pext V
U = q + w
H = U + ( PV )
C=

qrev
T

U = CV T

H = CP T

CP = CV + nR

S =

qrev
T

S 0

System changes, compute w,q, U, H, S (Cycles)


Chemical Reactions (Batteries) at Constant P and T
G = H TS

G = H T S

G = Grxn X

Q( X )
0
Grxn = Grxn
+ RT ln Q ( X ) = RT ln
K

o
1 1
H rxn
K2
ln
=

K1
R T2 T1

Grxn = nFECell

0
Grxn
= RT ln K

Thermodynamics
set of tools that describes the macroscopic properties of equilibrium
systems
entirely empirical science
based on four laws
0th law

1st law

2nd law

3rd law

defines
temperature

defines
energy

defines
entropy

provides a
numerical value
to entropy

Thermodynamics involves a lot of book-keeping, i.e. accounting for


energy/matter exchanges that help us predict the tendencies of
atoms and molecules to react, change their volume, their phase.

Carbon cycle

Thermodynamic cycles
Proton transport in ion channels
Nature 438, 975-980 (15 December 2005)

http://earthobservatory.nasa.gov/Library/CarbonCycle/Images/carbon_cycle_diagram.jpg

Otto engine

Energy is used to
generate heat; heat is
used (goes into the
engine) and generates
work; work comes out
of the engine. The
engine (the system) is
unchanged.

Definitions
System E.G.:
Gas in a box
Mass on a Spring
system
boundary
surroundings

Systems can be classified as:


Open: mass and energy can be transferred between system and
surroundings
Closed: energy can transfer but not mass
Isolated: Neither energy nor mass can be transferred between system
and surroundings

Definitions: What do we mean by energy in a system?


The energy is the sum of the kinetic and the potential energies.
We only look for changes in the energy.
Lets Consider the energy in a mass on a spring (the Harmonic Oscillator)
Follow the energy as an isolated system
Follow the energy when the mass can interact with the
surroundings.
Apply the same analysis to the gas in a cylinder (or box).

How do we describe a system at equilibrium?


Thermodynamic variables or state variables
temperature T, pressure P and volume V, moles n
Variables are extensive or intensive
Extensive
Sum of the properties of the systems components.
Depends on the size of the system
Volume (V), Area (A), # of moles (n)
Intensive
Independent of the size of the system
Temperature (T), Pressure (P) and concentration
We can define equations of state such as the Ideal gas law

PV = nRT

n
C=
V

n
P = RT
V

P = C RT

Identify the extensive and intensive variables.

m
d = = M C
V

Zeroth Law of Thermodynamics: definition of temperature

heat conducting wall

If A and C are at thermal equilibrium, i.e. at the same


temperature, and B and C are at thermal equilibrium, then it
follows that A and B are at thermal equilibrium, i.e. at the
same temperature.

Charles Law: Ideal gases can be thermometers

nR
P=
T
V

P = xT + g
g = 273.15C

At low density All Gasses behave


as ideal gasses

Ideal gases

PV = nRT = N A kT
n
P = RT = RT
V
k = Boltzmann constant
= density
A = Avogadros number
R = gas constant

=0
V T
H

=0
P T

Internal energy
and Enthalpy for
an ideal gas
depend only on
temperature

Isotherm at 700 K

Van der Waals Equation of state


Units of the constants?

nRT
na
P=
2
V nb V

n a
P + 2 (V nb ) = nRT
V

Pressure correction
accounts for
interaction potential
between molecules

Volume correction
accounts for finite
size of the gas
molecules

volume2 mole-2 pressure


Pa m6 mol-2
volume mole-1
m3 mol-1

Daltons Law of Partial Pressures: Ideal Gas Mixtures

Ptotal = P1 + P2 + P3 + ... = Pi
i

RT
Pi = ni
V

ni
i =
nTot

RT RT
PTot = Pi = ni
=
V
V
i
i

=1

Partial pressure
of the ith gas in
the mixture

RT
i ni = V nTot

Example: A mixture of 1 mole of methane and 4 moles of


ethane are held at a pressure of 10 bar. What are the mole
fractions and partial pressures of the two gases?

Ptotal = Pmethane + Pethane = 10bar


Ptotal RT Pi
=
=
ntotal
V
ni
Pi =

ni
Ptotal = xi Ptotal
ntotal

ntotal = nmethane + nethane = 1mole + 4moles = 5moles


Pmethane
Pethane

nethane
4moles
10bar = 8bar
=
Ptotal =
5moles
ntotal

xmethane
xethane

nmethane
1mole
10bar = 2bar
=
Ptotal =
5moles
ntotal

nmethane
=
= 0.2
ntotal

nethane
=
= 0.8
ntotal

Key points of todays lecture


 Thermodynamics describes macroscopic properties of equilibrium
systems
There are 4 laws of thermodynamics
Definitions: system, surroundings, boundary, state variables,
extensive, intensive properties
Definition of temperature: 0th law of thermodynamics
Defining a temperature scale
Ideal gases
Real gases
Partial pressures of ideal gasses

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