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You are on page 1of 14

**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 = hν Photon

P.E.Coul

Ze 2

=−

r

c = λν

**• 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.

Let’s 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 system’s 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

A

C

B

C

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 = −273.15°C

**At low density All Gasses behave
**

as ideal gasses

Ideal gases

PV = nRT = N A kT

n

P = RT = ρ RT

V

k = Boltzmann constant

ρ= density

A = Avogadro’s number

R = gas constant

∂U

=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?

2

nRT

na

P=

− 2

V − nb V

a

b

2

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

Dalton’s Law of Partial Pressures: Ideal Gas Mixtures

Ptotal = P1 + P2 + P3 + ... = ∑ Pi

i

RT

Pi = ni

V

ni

χi =

nTot

RT RT

PTot = ∑ Pi = ∑ ni

=

V

V

i

i

⇒

∑χ

i

=1

Partial pressure

of the ith gas in

the mixture

i

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 today’s 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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