Thermodynamics Thermal Physics Statistical Mechanics Deals with a collection of a large number of particles It is effectively impossible to follow the

the motion and trajectory of each particle In thermal physics, we combine two approaches thermodynamics statistical mechanics to understand and predict behavior
Thermodynamics: Phenomenological theory of matter Macroscopic theory (i.e. it doesnt contain information about atoms, molecules, ) Draws its concepts directly from experiment Always correct, cannot be questioned since they are deduced from experiment Does not depend upon microscopic details (e.g. 1st & 2nd laws, heat flow from hot to cold, maximum efficiency of engines) Statistical Mechanics Attempt to understand thermodynamical laws from interactions of atoms, molecules, and other microscopic degrees of freedom Fundamental laws of interaction Statistical theory of a (e.g. mechanics, quantum large collection mechanics, etc.) of particles Statistical concepts and certain basic assumptions1 Provides an underlying explanation of thermodynamics

Some of the basic assumptions cannot be proven easily.

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Two key concepts in Thermodynamics 1. Equilibrium 2. Temperature It is difficult to define these terms rigorously at this level. The following definitions will have to do for now: Equilibrium Equilibrium is reached when the thermodynamic state of the system does not change with time. e.g. when you bring two objects into contact for long enough time, they will be in equilibrium Temperature Temperature is a thing that is the same for two objects after they have been in contact for a long enough time; i.e. they are in thermal equilibrium. Temperature is a measure of the tendency of an object to spontaneously give up energy to its surroundings. An object at higher temperature tends to lose energy to an object at lower temperature. Well see shortly that temperature is related to the internal energy of a system. Internal energy consists of: atomic kinetic (translation, rotation, vibration) and potential energy (atomic interactions)

Temperature scale and units Choose something that changes with temperature e.g. thermal expansion Pick two convenient temperatures and assign them arbitrary numbers e.g. water boiling (100) and freezing (0) Mark off a number of equally spaced intervals in between the two end points and extrapolate above and below The ideal gas thermometer extrapolates to P = 0 at -273.15C

What is the physical meaning of P = 0 ? We define an absolute temperature scale

Tk = Tc 273.15

Use the ideal gas as an example to demonstrate the relationship State functions ( P,V , T ) microscopic property (velocity) Thermodynamics Statistical Mechanics (I) Thermodynamics of an Ideal Gas: The ideal gas law: PV = nRT

n = number of moles of gas R = universal gas constant = 8.31 J mol -1 K -1

1 mole = number of C12 atoms in 12 grams of C12 = 6.02 x 1023 Define N A = 6.02 1023 Avogadros number Then the total number of molecules in n moles of an ideal gas is N = nN A molecules. Define Boltzmanns constant k= Then R = 1.381 1023 J K -1 NA

( nR = Nk )

PV = nRT = nkN AT = ( nN A ) kT = NkT we can write either

PV = nRT

or

PV = NkT

1. The ideal gas is the thermodynamic system 2. P, V, T are state functions or thermodynamics parameters: measurable macroscopic quantities that define the state of the system
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3. PV = nRT = NkT This is an example of a thermodynamic equation of state (which is an equation that states the relationship between different state functions. In general, it is of the form f ( P,V , T ,K) = 0 ) 4. As a typical equation of state in thermodynamics, it is deduced from experiment (Not derived from theory) (II) Kinetic theory (from a microscopic model) of and Ideal gas:

x
Assumptions (i) Smooth walls symmetrical bounces (like a mirror) (ii) Molecules behave like elastic billiard balls bouncing around v x = v x has constant magnitude, although periodically changing direction (iii) Low density each molecule moves as if it is alone, i.e. non-interacting Goal: To relate the temperature of the gas to kinetic energy (K.E.) of molecules Approach: first, find how P is related to K.E., then use the ideal gas law (PV = NkT) to find the relationship between T + K .E.
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Consider one molecule Let v = velocity of the molecule v x = v x = x component of v Recall

F =

dp d ( mv ) dv = = m dt dt dt
-vx v
^ x

The average force on the piston (averaged over the period t between collisions) v F =m x t where v x = 2v x (in one collision)

vx

t = time interval between collisions 2L = vx Therefore 2 L = v x t 2v x m 2 F = m = vx 2L v x L The average pressure (force per unit area) F m 2 m 2 P= = vx = vx A LA V If there are many (N) molecules, then the total average pressure is 1 N mi = mass of the i th molecule P = mi vi2 x V i =1 th

v mN i=1 i = V N

2 i x

vix = x component of the i

molecules velocity

assuming the molecules to be identical (mi = m)

2 PV = Nmv x

where the average x-component of the velocity is v =

2 x 1 N

v
i =1

2 i x

Now

2 PV = Nmv x

PV = NkT We can identify

is a microscopic description (derived from laws of mechanics + some assumptions) is a macroscopic thermodynamic description (derived from experiment)

2 kT = mv x for an ideal gas; this is a microscopic interpretation of T

So

1 2

2 kT = 1 mv x 2

is the average Kinetic Energy associated with translational motion in the x-direction

We can derive the same expressions for motion in the y- and zdirections 1 1 2 1 1 2 kT = mv x = mv 2 = mv z y 2 2 2 2
2 The magnitude of the velocity vector is v 2 = v x + v 2 + v z2 y The average Kinetic Energy of molecules is

1 2 1 2 mv = mv x + mv 2 + mv z2 y 2 2 1 = ( kT + kT + kT ) 2 3 = kT 2

Therefore, we interpret temperature as the average kinetic . energy of the molecules divided by k. T ~ K kE . Define Thermal Energy (U th ) Thermal energy is the internal energy of a system that consists of the kinetic and potential energies associated with the motion and interactions of the atoms and molecules in the system.
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Equipartition Theorem At temperature T, the average thermal energy of each quadratic degree of freedom is kT This is an important theorem in classical statistical mechanics It will be proven later in the course (see Chapter 6)

Note: (i) It is not true in quantum statistical mechanics (which is important at low temperature) (ii) It is true for quadratic degrees of freedom only all types of kinetic energy e.g. 1 mv 2 , 1 I 2 (translational, rotational) 2 2 for potential energy, only good for harmonic oscillator, i.e. V ( x ) = 1 kx 2 2 Example: ideal gas (N molecules) 1 1 2 1 Total kinetic energy = N mv x + mv 2 + mv z2 y 2 2 2 1 1 1 = N kT + kT + kT 2 2 2

1 = N ( 3) kT 2 each degree of freedom (quadratic) 1 U thermal = N ( 3) kT has 1 2 kT average energy 2 3 degrees of freedom for simple (monoatomic) molecule corresponding to x, y , z translational motion In general, we have 1 where f = number of degrees U thermal = Nf kT 2 of freedom
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Counting f is tricky for complex molecules

(I) Consider CO (carbon monoxide) C O A good model is a hard bond connecting C and O

f = 5 = 3 translational + 2 rotational
C O

There should also be two additional degrees of freedom associated with the stretching of the CO bond 1 kinetic 2 vibrational 1 potential

but it is usually very difficult to stretch molecules. We say that the stretching mode is note normally excited at room temperature. We also say that it is frozen out.

(II) Spring model of a solid

f =6 Each atom has 6 degree of freedom 3 for kinetic, 3 for potential energy for small vibrations, the potential energy is like that for a harmonic oscillator (i.e. quadratic V ( x ) = 1 kx 2 ) 2
U thermal 1 = N 6 kT 2
U(r)
1 2

k ( r r0 )

This is true only at high temperature. At low temperature, some of the higher energy modes will be frozen out due to quantum effects. This will be discussed later.

r0

r atomic separation

This example shows that the equipartition theorem is very powerful and useful, but it is only strictly correct in the realm of classical physics and harmonic potentials.

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Heat, Work and the 1st Law of Thermodynamics Heat

are two different forms of energy transfer

Work Heat : Work :

the form of energy which is transferred from one object to another due to a difference of temperature between the objects transfer of energy to or from a system by a change of parameters that describe the system (other than temperature, e.g. push a piston, stir a cup, run a current through a resistor, etc.)

The internal energy, U, of a system is defined up to an arbitrary additive constant The change of internal energy, U, is always unambiguous
The First Law of Thermodynamics

U = Q + W where Q is heat added to the system W is work done on the system This is really just the Law of Conservation of Energy !

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Heat Historically, scientists did not always know that heat is a form of energy, until the famous Joules experiment demonstrated the equivalence of heat and work. Consequently, we use Joule as the SI unit for energy. 1 calorie is the amount of heat (Q) needed to raise the temperature of 1 gram of water by 1C (from 14.5 to 15.5C) 1 cal = 4.186 J 1 kcal = 4186 J Work There are different kinds of work (e.g. mechanical, electrical,) We focus on the simplest form of mechanical work. Consider a simple, idealized situation: ideal gas compression

Assumptions: (i) Quasi-static, which means that the motion of the piston is so slow that the system always has time to reach equilibrium (ii) No friction, which means that the piston does work on the gas only; no work is wasted in overcoming friction (iii) The change in volume is small so that the pressure remains nearly constant
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Calculate the work done on the gas when the piston is displaced a distance x to the left
W = F x = PAx = P ( Ax ) = P ( V )

V = V final Vinitial < 0 which means that W > 0

Usually, our assumption (iii) ( P = constant ) is not valid. If P changes with volume, then a more general expression for W is

dW = P dV
W = PdV
Vi Vf

where P = P (V ) is a function of V

W is the area under the curve

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Ideal Gas Compression: Two Kinds of Process 1) Isothermal: T remains constant for this to happen, the gas cylinder must be in contact with a heat bath (reservoir) of fixed temperature T, and the process must be slow enough that heat can be transferred to or from the reservoir much faster than work is being done on the gas. 2) Adiabatic: No heat can enter or leave the gas (Q = 0) ; (i) it is perfectly insulated, or (ii) the process happens so quickly that heat does not have a chance to leave of enter
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Isothermal process

PV = NkT P=
Vf Vi

NkT V

W = PdV dV Vi V = NkT ( ln V f ln Vi ) = NkT

Vf

Vi = NkT ln V f

For compression, Vi > V f W > 0 (the work done on the gas is positive)

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Isothermal compression (continued)

Lets find the heat added or removed during an isothermal compression of an ideal gas Use the 1st Law

recall Q is heat added to the system U = Q + W W is work done on the system

U = N f ( 1 kT ) equipartition theorem 2 U = N f ( 1 k T ) 2 =0 since T = 0 (isothermal)

Therefore

V Q = W = NkT ln i V f

For compression Vi > V f Q is negative Heat must leave the system during an isothermal compression. The amount of heat that leaves is equal to the work done on the system.

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Adiabatic process 0 U = Q + W For an ideal gas

1st Law

U = Nf ( 1 kT ) 2 dU = ( Nf 1 k ) dT 2 U = W dU = dW = PdV

eq. (1)

For adiabatic process

eq. (2)

Substitute eq. (1) into eq. (2)

Nf 1 kdT = PdV 2

Use the ideal gas law ( PV = NkT )

NkT Nf 1 kdT = dV 2 V f dT dV = 2 T V Solve this by integrating Vf f Tf ln = ln V 2 Ti i

Tf T i

f 2

V = i V f
= ViTi f

Vf Tf f

or VT f

= constant

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Adiabatic compression (continued)

Substitute for T from the ideal gas law

PV V Nk or P V PV
f 2 f 2

T =

PV Nk

= constant = constant = constant

f +2 2 f +2 f

PV = constant

f +2 f

is the adiabatic exponent

(PV = constant)

Isotherms:

PV = nRTf PV = nRTi

For an adiabatic compression, U = W W >0 T > 0

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Heat Capacity
C= Q T C m C n

Heat capacity is the ratio of the amount of heat added to a system to its corresponding temperature rise Specific heat capacity is the heat capacity per unit mass Molar heat capacity ( n = number of moles)

c= c =

Note that while U is independent of path or process (that means U is a state function it depends only on the initial and final states and not the path), both Q and W are generally path-dependent.
U = Q + W

(1st law)

Therefore, C is not well-defined unless one also specifies the process or path clearly. For an ideal gas, this means whether we just add or remove heat or whether we also do work on the gas at the same time. Using the 1st law, we can write
C= U W T

The two most common definitions (paths) are 1. CV = heat capacity at constant volume 2. CP = heat capacity at constant pressure

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1 Heat capacity at constant volume, CV Since volume is constant P

W = P dV = 0

Tf Ti V

U U = CV = T V T V

we can also call this the Energy capacity

this means at constant volume

For an ideal gas

U = Nf

( 1 kT ) 2

Nfk U CV = = 2 T V
3 e.g. for a monoatomic gas f = 3 CV = 2 Nk 3 = 2 nR

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2 Heat capacity at constant pressure, C P At constant pressure, P volume is not constant and work is not zero
W = P dV = P dV = P V

Tf Ti V

CP =

U W U + PV = T T U V = + P P 4T 4 1 24P T 3 123 4
This term describes the part of the heat added that is used to do work of expansion

This term describes the part of the heat added that causes the internal energy to increase

CP > CV
For ideal gas ( PV = NkT ), the second term is
V P = Nk T P

and the CP is

f + 2 f + 2 = nR CP = CV + Nk = Nk 2 2

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V is small, so that we can take CV and CP T to be approximately equal CV CP

For solids and liquids,

For a solid, f = 6 (K.E. and P.E. in x, y, and z)

6 CV = N k = 3Nk = 3nR 2 (or c = 3R = 24.9 J mol K ) C n

This is called the Dulong and Petit rule. It is true for all solids, provided the temperature is high (compared to something called the Debye temperature every material has a different unique Debye temperature). At low temperature, Quantum effects become important!

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Latent Heat As a phase transition (e.g. ice water, water stream), the system takes in or releases heat, but the temperature remains constant. During the transition, latent heat is used to break chemical bonds rather than increasing the kinetic energy of atoms. So, at the phase transition temperature, Tc, the heat capacity diverges
C= Q Q = = T 0

Diverging C is commonly used to identify phase transitions Q Latent heat is defined as L = , m i.e. the heat needed to transform the system from one phase to another phase In order that L is well defined, the convention is that 1. P is constant (usually 1 atm) 2. no other work is done besides the mechanical work of constant pressure expansion or compression For example Ice melting Water boiling Compare to Water (0C 100C)
Q = 100 cal g m L = 80 cal g L = 540 cal g

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Enthalpy Define Enthalpy (H):

H = U + PV
internal energy work needed to create room for the system

Enthalpy is useful for considering energy changes under constant pressure conditions. Under normal conditions, P is usually constant (e.g. 1 atm). If a system is changed from one state to another, due to external work or heat, then the external energy input will serve to 1. increase the internal energy by dU , and 2. do work against (atmospheric) pressure, if the volume changes as well, by PdV
P P P energy input (heat or work) P P P P external pressure (P) P system P P volume expands (dV) P P P PdV is associated with this part

dH = dU + PdV

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Enthalpy continued
P P

P volume expands (dV) P

dH = dU + PdV

energy input (heat or work) P P

system

P P PdV is associated with this part

P P external pressure (P)

Recall the 1st Law where we have used

total work

dU = Q + W = Q + ( PdV ) + Wother
W = PdV + Wother
work done by compression any other form of work done on the system (besides volume change; e.g. electrical, chemical)

Therefore

dH = dU + PdV = Q + Wother

This means that the enthalpy change is caused only by heat and other forms of work, not compression-expansion work. If Wother = 0 , then dH = Q Recall (from pg. 20 of these notes or eq. 1.45 in the text book) U ( PdV ) U + PdV H CP = = = T T P T P P or H CP = = enthalpy capacity T P which is similar to U CV = = energy capacity T V
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Example: the enthalpy change associated with boiling water

It is customary for chemists to be concerned with H of chemical reactions because there is usually a substantial change of volume and the reaction takes place in a laboratory at constant (atmospheric) pressure. Boiling water at 100C, 1 atm
1 mole ~ 18 g steam (water vapor) at 1 atm H

Heat Source

H = 40660 J for 1 mole (18 g) Q Note H 18 = 2260 J is the Latent Heat L = m for the transformation
The enthalpy change for this reaction can be written

H = U + P V V = Vsteam Vwater ~ Vsteam

Hence
PV PVsteam

(Vsteam >> Vwater )

Treat steam as an ideal gas

PV = RT = ( 8.31 J K ) ( 373 K ) = 3100 J

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This means that out of the H = Q = 40660 J ,

3100 8% 40660

of the heat energy is used to push the atmosphere away to make room for the water vapor.

40660 3100 92% 40660

of the heat energy is used to break the chemical bonds between the H2O molecules in liquid so that the escape into a gaseous form.

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Another Example: Enthalpy of Formation

gas (1.5 mole total)

1 H 2 + O 2 H 2O H { 1 24 4 23 liquid

1 O 2 (gas) has more internal energy than (liquid) water, so 2 when hydrogen burns to form water, it releases 286 kJ/mole of water produced. H = 286 kJ Enthalpy This means that enthalpy decreases, of Formation H2 +
heat is released (exothermic)

Like the previous example, the volume of the liquid is negligible compare to the volume of the gas. Therefore H = U + PV = U + PVgas Formation of 1 mole of water requires 1 mole of H2 and 0.5 mole of O2, which means a total of 1.5 mole of gas. The work done on the gas when it collapses to form water is
PVgas = nRT = (1.5) (8.31 J mol -1 K -1 ) ( 300 K )

~ 4 kJ

Therefore, of the H = Q = 286 kJ produced, 4 kJ comes from the work done and the rest (282 kJ) comes from the change of chemical bonds.

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