Lecture 2 The First Law of Thermodynamics (Ch.

1) Outline:
1. Internal Energy, Work, Heating 2. Energy Conservation the First Law 3. Quasi-static processes 4. Enthalpy 5. Heat Capacity

Internal Energy
The internal energy of a system of particles, U, is the sum of the kinetic energy in the reference frame in which the center of mass is at rest and the potential energy arising from the forces of the particles on each other.
system boundary Difference between the total energy and the internal energy?

system

U = kinetic + potential

environment
B P V

The internal energy is a state function it depends only on the values of macroparameters (the state of a system), not on the method of preparation of this state (the path in the macroparameter space is irrelevant).

In equilibrium [ f (P,V,T)=0 ] :

U = U (V, T)

U depends on the kinetic energy of particles in a system and an average inter-particle distance (~ V-1/3) interactions. For an ideal gas (no interactions) :

U = U (T) - pure kinetic

Internal Energy of an Ideal Gas

The internal energy of an ideal gas with f degrees of freedom:

f U ! Nk BT 2

f 3 (monatomic), 5 (diatomic), 6 (polyatomic) (here we consider only trans.+rotat. degrees of freedom, and neglect the vibrational ones that can be excited at very high temperatures) How does the internal energy of air in this (not-air-tight) room change with T if the external P = const?

U!

f PV f N in room k BT ! N in room ! ! PV 2 k BT 2

- does not change at all, an increase of the kinetic energy of individual molecules with T is compensated by a decrease of their number.

Work and Heating (Heat)

We are often interested in (U , not U. (U is due to: Q - energy flow between a system and its environment due to (T across a boundary and a finite thermal conductivity of the boundary heating (Q > 0) /cooling (Q < 0) (there is no such physical quantity as heat; to emphasize this fact, it is better to use the term heating rather than heat) W - any other kind of energy transfer across boundary - work

WORK

HEATING

Work and Heating are both defined to describe energy transfer across a system boundary. Heating/cooling processes: conduction: the energy transfer by molecular contact fast-moving molecules transfer energy to slow-moving molecules by collisions; convection: by macroscopic motion of gas or liquid radiation: by emission/absorption of electromagnetic radiation.

The First Law

The first law of thermodynamics: the internal energy of a system can be changed by doing work on it or by heating/cooling it.

(U = Q + W

conservation of energy.

Sign convention: we consider Q and W to be positive if energy flows into the system. For a cyclic process (Ui = Uf) Q = - W. If, in addition, Q = 0 then W = 0
P

An equivalent formulation: Perpetual motion machines of the first type do not exist.

Quasi-Static Processes
Quasi-static (quasi-equilibrium) processes sufficiently slow processes, any intermediate state can be considered as an equilibrium state (the macroparamers are welldefined for all intermediate states). Advantage: the state of a system that participates in a quasi-equilibrium process can be described with the same (small) number of macro parameters as for a system in equilibrium (e.g., for an ideal gas in quasiequilibrium processes, this could be T and P). By contrast, for nonequilibrium processes (e.g. turbulent flow of gas), we need a huge number of macro parameters. Examples of quasiequilibrium processes: isochoric: isobaric: isothermal: adiabatic: V = const P = const T = const Q=0
For quasi-equilibrium processes, P, V, T are well-defined the path between two states is a continuous lines in the P, V, T space. P 2 V

1 T

Work
A the
piston area

The work done by an external force on a gas enclosed within a cylinder fitted with a piston:

W = (PA) dx = P (Adx) = - PdV

force

(x

The sign: if the volume is decreased, W is positive (by compressing gas, we increase its internal energy); if the volume is increased, W is negative (the gas decreases its internal energy by doing some work on the environment).

W1 2 !  P(T , V ) dV
W = - PdV - applies to any shape of system boundary
V1

V2

dU = Q PdV

The work is not necessarily associated with the volume changes e.g., in the Joules experiments on determining the mechanical equivalent of heat, the system (water) was heated by stirring.

W and Q are not State Functions

W1 2 !  P (T ,V )dV
V1 V2

- we can bring the system from state 1 to state 2 along infinite # of paths, and for each path P(T,V) will be different.

2 V

1 T

Since the work done on a system depends not only on the initial and final states, but also on the intermediate states, it is not a state function. U is a state function, W - is not thus, Q is not a state function either.

(U = Q + W
P
P2 P1
A B

Wnet ! WAB  WCD !  P2  2  V1  P1  1  V2 V V ! P2  P1  2  V1 0 V

V1

V2

PV diagram

- the work is negative for the clockwise cycle; if the cyclic process were carried out in the reverse order (counterclockwise), the net work done on the gas would be positive.

Comment on State Functions

U, P, T, and V are the state functions, Q and W are not. Specifying an initial and final states of a system does not fix the values of Q and W, we need to know the whole process (the intermediate states). Analogy: in classical mechanics, if a force is not conservative (e.g., friction), the initial and final positions do not determine the work, the entire path must be specified. In math terms, Q and W are not exact differentials of some functions of macroparameters. To emphasize that W and Q are NOT the state functions, we will use sometimes the curled symbols H (instead of d) for their increments (HQ and HW). U

d U ! T d S  P dV
y z(x1,y1)

V S

- an exact differential

- it is an exact differential if it is the difference between the values of some (state) function z(x2,y2) dz ! z x  dx, y  dy  z x, y z(x,y) at these points: xAx x, y xAy x, y x ! A necessary and sufficient condition for this: xy xx xz x, y xz xz x, y If this condition xz Ax x, y ! Ay x, y ! d z ! dx  dy xy holds: xx xy xx y x

dz ! Ax x, y dx  Ay x, y dy

e.g., for an ideal gas:

T f HQ ! dU  PdV ! Nk B dT  dV V 2

- cross derivatives are not equal

Problem
Imagine that an ideal monatomic gas is taken from its initial state A to state B by an isothermal process, from B to C by an isobaric process, and from C back to its initial state A by an isochoric process. Fill in the signs of Q, W, and (U for each step. P, 105 Pa 2 Step
A

Q + -+

W -+ 0

(U 0 -+

T=const
B C

ApB BpC

CpA 2 V, m3

f U ! Nk BT 2

PV ! Nk B T

Quasistatic Processes in an Ideal Gas

P 2 PV= NkBT2 PV= NkBT1 V1,2 V isochoric ( V = const )

W1p2 ! 0

Q1p2

3 ! Nk B T2  T1 " 0 2

! CV (T

dU ! Q1p2
isobaric
2

(see the last slide) ( P = const )

P 2 1 V1 V2 PV= NkBT2 PV= NkBT1 V

W1p2 !  P(V , T )dV !  P 2  V1 0 V

1

5 Q1p2 ! Nk B T2  T1 " 0 2

! CP (T

dU ! W1p2  Q1p2

Isothermal Process in an Ideal Gas

P PV= NkBT

isothermal ( T = const ) :

dU ! 0
W1p2 !  P (V , T )dV !  Nk BT
V1 V2 V2

W
V2 V1 V

dV V !  Nk BT ln 2 V V1 V1

Wi  f

Vi ! Nk BT ln Vf

Q1p 2 ! W1p2

Wi-f > 0 if Vi >Vf (compression) Wi-f < 0 if Vi <Vf (expansion)

Adiabatic Process in an Ideal Gas

adiabatic (thermally isolated system)

Q1p2 ! 0
V2

dU ! W1p2

The amount of work needed to change the state of a thermally isolated system depends only on the initial and final states and not on the intermediate states.

P 2 PV= NkBT2 PV= NkBT1 V

W1p2 !  P(V , T ) dV
V1

to calculate W1-2 , we need to know P (V,T) for an adiabatic process

1 V2 V1

f U ! Nk BT 2

f dU ! Nk B dT !  PdV 2
2 PdV z PV f V P dV dP  !0 K V P1 P V1

( f the # of unfrozen degrees of freedom )

PV ! Nk BT
dV V

PdV  VdP ! Nk B dT

PdV  VdP ! 
2 Adiabatic f exponent

2 dP 1   P !0 f
K

K ! 1

V P K ln ! ln 1 PV K ! P1V1 ! const V P 1

Adiabatic Process in an Ideal Gas (cont.)

P 2 PV= NkBT2 PV= NkBT1 V
V2

PV K ! P1V1 ! const
An adiabata is steeper than an isotherma: in an adiabatic process, the work flowing out of the gas comes at the expense of its thermal energy its temperature will decrease.
K 1 1 K V2

1 V2 V1
V2

W1p2

1 PV K !  P (V , T )dV !  dV !  PV1 V  K 1 1 K  1 V V1 V1 V1

1 1 1 ! PV K 1  K 1 K  1 V2 V1
K 1 1

1+2/3}1.67 (monatomic), 1+2/5 =1.4 (diatomic), 1+2/6 }1.33 (polyatomic) (again, neglecting the vibrational degrees of freedom)

Prove W1p2

f f ! ( PV ! Nk B (T ! (U 2 2

Summary of quasi-static processes of ideal gas

(U | U f  U i

Ideal gas Quasi-Static Q W (U law process f f f 2 isobaric Vi V f (U ! Nk B (T ! P(V  P(V P(V ! 2 2 2 Ti T f ((P=0) Pi Pf isochoric (U ! f Nk (T ! f (P V f (P V !   0 B Ti T f 2 2 2 ((V=0) Vf isothermal PVi ! Pf V f  Nk BT ln W i 0 Vi ((T=0) f f adiabatic PVi K ! Pf V fK i (U ! Nk B (T ! ( PV (U 0 2 2 (Q=0)

Problem
Imagine that we rapidly compress a sample of air whose initial pressure is 105 Pa and temperature is 220C (= 295 K) to a volume that is a quarter of its original volume (e.g., pumping bikes tire). What is its final temperature? Rapid compression approx. adiabatic, no time for the energy exchange with the environment due to thermal conductivity

PV1 ! Nk BT1 1 P2V2 ! Nk BT2 PV1K ! P2V2K 1

PV1K P2 ! 1 K V2

PV1K PV 1 ! Nk BT2 ! 1 1 T2 V2K 1 T1

V 1 V 2
K 1

K 1

T2 T1

For adiabatic processes:

T1 V
also

K 1 1

! T2 V2

! const

V1 T2 ! T1 V 2

K 1

P K 1 / T K ! const

! 295 K v 40.4 } 295 K v 1.74 } 514 K

- poor approx. for a bike pump, works better for diesel engines

Non-equilibrium Adiabatic Processes Free expansion

1.

TV K 1 ! const

V increases T decreases (cooling)

2.

On the other hand, (U = Q + W = 0 U ~ T T unchanged (agrees with experimental finding) Contradiction because approach #1 cannot be justified violent expansion of gas is not a quasistatic process. T must remain the same.

TV K 1 ! const

- applies only to quasi-equilibrium processes !!!

The Enthalpy
Isobaric processes (P = const): dU = Q - P(V = Q -((PV) Q = ( U + ((PV)

H | U + PV - the enthalpy

The enthalpy is a state function, because U, P, and V are state functions. In isobaric processes, the energy received by a system by heating equals to the change in enthalpy. isochoric: isobaric: Q=(U Q=(H
in both cases, Q does not depend on the path from 1 to 2.

Consequence: the energy released (absorbed) in chemical reactions at constant volume (pressure) depends only on the initial and final states of a system. The enthalpy of an ideal gas: (depends on T only)

f f H ! U  PV ! Nk BT  Nk BT !  1 Nk BT 2 2

Heat Capacity
The heat capacity of a system - the amount of energy transfer due to heating required to produce a unit temperature rise in that system T C is NOT a state function (since Q is not a state function) it depends on the path between two states of a system ( isothermic C = g, adiabatic C = 0 )
T1+dT T1

HQ C| (T
f1 f2 f3

The specific heat capacity

C c| m

CV and CP
xU the heat capacity at CV ! xT V constant volume xH CP ! xT P
the heat capacity at constant pressure

HQ dU  PdV C! ! dT dT

To find CP and CV, we need f (P,V,T) = 0 and U = U (V,T)

f f H !  1 Nk BT For an ideal gas U ! Nk BT 2 2 f f f CP !  1 nR CV ! Nk B ! nR 2 2 2

# of moles For one mole of a monatomic ideal gas:

3 5 CV ! R C P ! R 2 2

Another Problem
During the ascent of a meteorological helium-gas filled balloon, its volume increases from Vi = 1 m3 to Vf = 1.8 m3, and the pressure inside the balloon decreases from 1 bar (=105 N/m2) to 0.5 bar. Assume that the pressure changes linearly with volume between Vi and Vf. (a) If the initial T is 300K, what is the final T? (b) How much work is done by the gas in the balloon? (c) How much heat does the gas absorb, if any?

P Pi Pf

Vi

Vf

P ! 0.625 bar/m3 v V  1.625 bar V

(a)

PV ! Nk B T
Vf

PV T! Nk B

0.5bar v 1.8m 3 T f ! Ti ! 300K ! 270K Pi Vi 1bar v 1m 3 Pf V f

Vf

(b) HWON

!  P(V )dV - work done on a system HWBY ! P(V )dV - work done by a system
Vi Vi

HWON ! HWBY HWBY ! P (V )dV !  .5 v 0.8 bar m3  0.5 v 0.4 bar m3 ! 0.6bar m3 ! 6 10 4 J 0

Vf

(c)

(U ! HQ  HWON

Vi

HQ ! (U  HWON !

T 3 3 Nk B  f  Ti  WON ! Pi Vi f  1  HWBY ! 1.5 105 J v  0.1  6 10 4 J ! 4.5 10 4 J T T 2 2 i