CHAPTER 1

Thermodynamics

PHYSICAL CHEMISTRY
Physical chemistry: Study of the physical principles that determine the properties and behavior of chemical systems Microscopic viewpoint: Use of the concept of atoms and molecules Macroscopic viewpoint: Large-scale properties of matter without using the concept of molecules Thermodynamics: Study of inter-relationships among macroscopic properties of systems in thermodynamic equilibrium. Phenomenology based on laws. No explicit consideration of time and molecules. Thermodynamic equilibrium: macroscopic properties do not vary in time (more precise later) Thermodynamics Statistical mechanics Quantum chemistry

Kinetics
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THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

surroundings

THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system matter energy

surroundings

A system can be Open: can exchange matter and energy with surroundings

THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

energy

surroundings

A system can be Open: can exchange matter and energy with surroundings Closed: can exchange energy with surroundings

THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

surroundings

A system can be Open: can exchange matter and energy with surroundings Closed: can exchange energy with surroundings Isolated: cannot exchange either matter or energy
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THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

surroundings

A system can be separated from its surrounding by various kinds of walls Rigid or nonrigid: volume can/cannot change

THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

surroundings

A system can be separated from its surrounding by various kinds of walls Rigid or nonrigid: volume can/cannot change Permeable of impermeable: matter can/cannot pass through it

THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system heat

surroundings

A system can be separated from its surrounding by various kinds of walls Rigid or nonrigid: volume can/cannot change Permeable or impermeable: matter can/cannot pass through it Adiabatic or nonadiabatic: can/cannot conduct heat
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THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

surroundings Different types of equilibrium Mechanical equilibrium: no unbalanced forces act on or within the system

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THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

surroundings Different types of equilibrium Mechanical equilibrium: no unbalanced forces act on or within the system Material equilibrium: no net chemical reactions occur within the system; no transfer of matter occurs from one part of the system to another or between the system and its surroundings

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THERMODYNAMICS
System: Macroscopic part of the universe under study in thermodynamics Surroundings: Parts of the universe that can interact with the system

system

surroundings Different types of equilibrium Mechanical equilibrium: no unbalanced forces act on or within the system Material equilibrium: no net chemical reactions occur within the system; no transfer of matter occurs from one part of the system to another or between the system and its surroundings Thermal equilibrium: no change of the properties of the system or surroundings when they are separated by a thermally conducting wall
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THERMODYNAMICS
Macroscopic properties: average over many molecules and long times (energies >> individual molecular energies)

system

surroundings

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THERMODYNAMICS
Macroscopic properties: average over many molecules and long times (energies >> individual molecular energies)

half size system

half mass half volume surroundings

Properties Extensive: depend on the size of the system (e.g., mass, volume)

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THERMODYNAMICS
Macroscopic properties: average over many molecules and long times (energies >> individual molecular energies)

half size system

same density same temperature surroundings

Properties Extensive: depend on the size of the system (e.g., mass, volume) Intensive: do not depend on the size of the system (e.g., density, temperature)
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THERMODYNAMICS
Macroscopic properties: average over many molecules and long times (energies >> individual molecular energies)

system

surroundings

Systems Homogeneous: each intensive property has the same value throughout the system

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THERMODYNAMICS
Macroscopic properties: average over many molecules and long times (energies >> individual molecular energies)

system

phases

surroundings

Systems Homogeneous: each intensive property has the same value throughout the system Heterogeneous: a system composed of more than 2 phases Phase: a homogeneous part of the system
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THERMODYNAMICS
Macroscopic properties: average over many molecules and long times (energies >> individual molecular energies)

system 2 system 1

surroundings

same value of every thermodynamic property in system 1 and system 2

same thermodynamic state

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THERMODYNAMICS
Macroscopic properties: average over many molecules and long times (energies >> individual molecular energies)

system 2 system 1

surroundings

A thermodynamic state is defined in terms of intensive properties

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THERMODYNAMICS
Thermodynamic equilibrium (1) Intensive properties independent of time over macroscopic time scales (2) No matter or energy currents in the interior or at the boundaries of the system over such time scales (3) Attainable from a variety of directions

system , T

surroundings

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THERMODYNAMICS
Thermodynamic equilibrium (1) Intensive properties independent of time over macroscopic time scales (2) No matter or energy currents in the interior or at the boundaries of the system over such time scales (3) Attainable from a variety of directions

Steady state Only (1) is true

system

surroundings

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THERMODYNAMICS
Thermodynamic equilibrium (1) Intensive properties independent of time over macroscopic time scales (2) No matter or energy currents in the interior or at the boundaries of the system over such time scales (3) Attainable from a variety of directions O2 system H2

Steady state Only (1) is true

Metastable state Apparent equilibrium

surroundings

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THERMODYNAMICS
Thermodynamic equilibrium (1) Intensive properties independent of time over macroscopic time scales (2) No matter or energy currents in the interior or at the boundaries of the system over such time scales (3) Attainable from a variety of directions true equilibrium includes H2O O2 Steady state system Only (1) is true H2 H 2O surroundings

Metastable state Apparent equilibrium

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THERMODYNAMICS
Thermodynamic equilibrium (1) Intensive properties independent of time over macroscopic time scales (2) No matter or energy currents in the interior or at the boundaries of the system over such time scales (3) Attainable from a variety of directions

Experimental fact The thermodynamic state of a system is specified by a small subset of the intensive properties. The relation varies from system to system and is called the equation of state. Difficult to determine e.g., for a single component, homogeneous system: P and T are sufficient for a N-component, homogeneous system: P, T, x1, x2, ..., xN-1 (x = mole fraction)

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TEMPERATURE
If the states of the systems change they were not in thermal equilibrium. system 2 system 1 Temperature is the property defined to measure this behavior If/when they do not change they are in thermal equilibrium.

surroundings

Zeroth law of thermodynamics

(1) If A and C are in thermal equilibrium and (2) B and C are in thermal equilibrium, then A and B are in thermal equilibrium Temperature scale Celsius (Centigrade): based on ice point of water at 1 atm = 0 C steam point of water at 1 atm =100 C Thermodynamic (Kelvin): ice point = 273.15 K

K = C + 273.15 1K=1C
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IDEAL GASES
No interactions between molecules

2 > 1

Boyles law

P V = constant
(at constant T and mass)

real gases PV For real gases, it holds better and better as P 0 (i.e., at very low density) P
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IDEAL GASES
No interactions between molecules

Charles law

V = a1 + a2
(at constant P and mass)

Volume

Temperature An increase in temperature means the molecules are moving faster and hitting the walls harder and more often. Therefore, the volume must increase if the pressure is to remain constant.

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IDEAL GASES
No interactions between molecules

Temperature scale
Any ideal gas is predicted to have zero volume at the same temperature -273.15 C International agreement:

T = BV

Volume

Temperature

B is defined using the triple point of water:

Ttr = 273.16 K K = T C = T 273.15

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V T = (273.16 K ) lim P 0 Vtr

IDEAL GASES
Ideal-gas law
Combine Boyles and Charles law:

P V = constant V = a1 + a2 T

P1 , V 1 , T 1 P2 , V a , T 1 P 2 , V 2 , T 2 P1 V 1 = P 2 V a Va = BT1 V2 = BT2

P1 V 1 P2 V 2 = T1 T2 PV = constant T
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IDEAL GASES
Gay-Lussac + Avogadro

PV = constant = R n T

R = gas constant = 8.314 J mol-1 K-1 n = number of moles

Ideal gas mixtures

P V = ntot RT
Partial pressure

ntot = n1 + n2 + . . .

ntot

PV = RT

Pi = xi P
molar fraction:

ni xi = ntot

RT Pi = n i V
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EQUATIONS OF STATE
For homogeneous systems, when P and T are specified, then the volume also is specified

Equation of state:

V = f (P, T, n1 , n2 , . . . )

For ideal gases:

RT RT V = ntot = (n1 + n2 + . . . ) P P

For one-phase one-component system

V = nf (P, T )

Vm

V = n

Vm = f (P, T )

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EQUATIONS OF STATE
Real systems
For gases: van der Waals equation

an2 P 2 V

(V nb) = nRT
2

nRT n a P = + 2 V nb V
For liquids and solids (at ordinary temperatures and pressures)

Vm = c1 + c2 T + c3 T 2 c4 P c5 P T
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EQUATIONS OF STATE
Different equations of state

Constant temperature: isotherms Constant pressure: isobars Constant volume: isochores

Thermodynamics allows us to relate many properties to partial derivatives of P, Vm and T

Vm = f (P, T ) P = f (Vm , T ) T = f (Vm , P )

Vm T P Vm T Vm

Vm P
P T

Vm

T P

Vm

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EQUATIONS OF STATE
Vm = f (P, T ) P = f (Vm , T ) T = f (Vm , P )
Vm T P Vm T Vm Vm P
P T

Vm

T P

Vm

Only two are independent because

x y

=
z

1
y x z

x y

y z

z x

= 1
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EQUATIONS OF STATE
1 (T, P ) = V V T

Expansion coefficient:

P,n

Isothermal compressibility:

1 (T, P ) = V

V P

T,n

What is the isothermal compressibility of an ideal gas?

P V = nRT 1 (T, P ) = P
For real systems

gas > liquid > solid

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QUESTIONS

The planet earth is

closed or open isolated or nonisolated

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QUESTIONS
How many phases are there in a system that consists of 2 pieces of CaCO3(s), one piece of CaO(s) and 2 moles of CO2(g) ?

1 2 3 4

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SUMMARY

System & Surroundings Types of equilibria (mechanical, material, thermal) Properties (intensive vs. extensive) Ideal gas (Boyles, Charles, Gay-Lussac laws) Equations of state

Review: Differential and integral calculus

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