Thermodynamics – 1st Law (Chapter 19.

1- 3)
There are three basic laws of Thermodynamics developed and
formulated ~ two centuries ago.
It is a classical theory, developed completely independent of
atomic and molecular theory. It is remarkable to note that there
are no known exceptions to these three laws.
Some basic definitions before we start:
System Boundary Surroundings
Separates system rest of the universe
What we’re from surroundings
interested in Boundaries of a system come in 3 types in
studying. terms of what can be transferred.
Open Closed Isolated

Transferred Heat, matter Heat Nothing

Example Open beaker, or the oil Tin Can Perfect thermos

layer touching a water bottle
layer in that beaker
The first law is primarily concerned with three things: energy, heat, and
work. In its essence, the first law is the conservation of energy.
Energy, heat, and work all have the same units, Joules, so they all must
be related.
Let’s start first with heat. Begin with
The Zeroth Law of Thermodynamics :
When two systems A and B are in thermal equilibrium, they
have the same temperature.
If A and B have different temperatures and are placed in thermal
contact, heat will flow from the warm body to the cold body until they
reach thermal equilibrium and have the same temperature.
When heat, q, flows into our system, this is considered to be a
positive quantity. The converse also applies; heat leaving the
system is a negative quantity.
Heat flow will change the temperature of the system.
Let’s move on to work. This is a quantity from Classical Mechanics.
work = Force × distance M=Mass
Lifting a weight against gravity: w = − Mgh g=gravitational constant,
h=height lifted
Stretching a bond, or a rubber band: w = − F ⋅ l F=Force
l=length stretched
Changing a volume: w = − P∆V
Sign convention for work should be consistent with that used for
heat. When work is done by system on surroundings, this is a
negative quantity. Conversely, work done on a system is positive.
Heat added +q Heat removed -q
Work done on system +w Work done by system -w
Example from text (Fig. 19.1)

Initial Final Initial Final

System does work on surroundings (-w) Surrounding does work on system (+w)
w = − P∆V (∆V positive) w = − P∆V (∆V negative)
Let’s look at the sign conventions. The force (pressure) is measured from
the point of view of the external world, the volume (or length) from the
point of view of the system.
P + ∆ V + so work is negative (energy
w = − P∆V leaves system
Initial Final

P + ∆ V – so work is positive (energy

Initial Final enters system
Next a block of rubber (block so we can safely squeeze it) (or a chemical bond)
(F +)(∆l +) so work is negative (energy
Initial Final leaves system
Squeezed Relaxed
(F –)(∆l –) so work is negative (energy
Initial Final leaves system
Stretched Relaxed w = −F ⋅ l
(F –)(∆l +) so work is positive (energy
Initial Final enters system
Relaxed Stretched
(F +)(∆l –) so work is positive (energy
Initial Final enters system
Relaxed Squeezed
What about gravity? What is “the system”? Is it just the weight you
hold?
NO!

It is the Earth-weight system.

It is just like a rubber band except that it is always stretched.
So lifting something up raises energy of the system.
Lowering something lowers energy of the system.
There are other forms of work:
Electrical : w = φ dQ where Q is electrical charge (in Coulombs) and
φ is potential in Volts
Surface Tension : w = γ dA where A is area and γ is surface tension
Magnetic work (messy formulation)
 Vf
General expression: w=-∫ Pext dV ( Pext can vary with V )
Vi

Note that the value of w depends on Pext.

In both cases, the gas is compressed from
1.0 to 0.5 dm3, but b) has more work done
on the system. You can exert more force
on a gas than the static internal pressure!

Fig. 19.2
Now, consider the following effect on a beaker of water:
∆

298K 308K
System is the same after both interactions with surroundings. You can’t tell whether
work or heat was responsible for the system change.
(Move a spoon back and forth, the force is the external force on the spoon, the
distance is how far it travels, back and forth, to the spoon it looks like the bottom
panel on the rubber block example)
So, there must be some property of the system that can be altered by
heat or work in the same manner
Energy, U.
For both operations (work and heat) ∆U = U f − U i is independent of path
taken, and only depends on the initial and final states of the system.
Hence, U is called a state function
Heat and work are not state functions, they are path-dependent. (You
already saw this from Fig. 19.2 for the case of work.)
2
w = − ∫ Pext dV clearly depends on Pext
1

A ‘special’ path occurs when Pext is ‘just enough ’ to compress the gas
at every step along the path. This is called the reversible path.
The system stays in equilibrium.
This is an idealized process, since it would
take an infinitely long time to occur.
How does a system “know” whether a process is reversible or not?
The key is that a reversible process has to be “slow”.
If you slowly push on a plunger on a gas cylinder, the whole gas has time to stay at
equilibrium. But if you push real fast, which you have to get a higher external
pressure than internal, the piston accelerates and you pile up gas at high pressure
near it. When the piston stops you start generating shock waves as the compressed
gas expands. These contain the “extra” energy, and eventually dissipate as heat.
If you pull out on the piston real fast, the gas adiabatically expands, turning heat
energy into directed kinetic energy. Eventually, after the piston stops, the front hits
it, generating another shock wave which then dissipates as heat.

Another way to express “slow” is that the change has to be “small”: an external
force is only slightly different from the internal one, or a wall doing heating or
cooling is only slightly different T from the system.
This means that a slight change in the external situation will reverse the
direction of the process. Thus the word “reversible”.
 2
Energy is a state function. ∆U = ∫ dU = U 2 − U1 path independent
1

2
Work is not a state function. w = ∫1 δ w ≠ w2 − w1 path dependent
2
Heat is not a state function. q = ∫ δ q ≠ q2 − q1 path dependent
1

But, dU = δ q + δ w 1st Law of Thermodynamics as an

or ∆U = q + w equation: Conservation of Energy
Another way to characterize a function as a “state function” or not is to note that

∫ dU = 0 =∫ d ( state fn) while

∫ dq or ∫ dw or ∫ d (not state fn) need not be zero

The little circle on the integral means over a cycle: the ending point is the same as
the starting point.
But what about the Uncertainty Principle? δ Eδ t ≥ ℏ / 2 (t is time)
Yes, but for every upward fluctuation, there is a corresponding downward one.
This law really is universal (literally .... though when General Relativity comes
in, it takes a lot of thought. Prof. Hawking won a Nobel Prize for doing so.)
 Vf
General expression: w=-∫ Pext dV ( Pext can vary with V )
Vi

Note that the value of w depends on Pext.

You can exert more force on a gas than

the static internal pressure! An thus put
more work (energy) into the system. The
pictures at left are compressions.
Fig. 19.2

Or you can do the work reversibly, the

external pressure equaling the internal. In
this case the figure could be either
compression of expansion.
In an expansion, the work done by the
system is less, in absolute magnitude, than
the reversible work.
In either case, with signs taken into
account, w ≥ wrev , the work being
measured with respect to the system
 Ideal gases as model thermodynamic systems
We need their properties.
What is an ideal gas? Answer: an ideal gas is a gas of noninteracting
particles (i.e. not colliding) obeying Boltzmann statistics.
In Chem. 442 we proved using the quantum Particle in a Box
wavefunctions, the Adiabatic Theorem, and Boltzmann statistics that
ideal structureless particles (atoms) obey the equation of state
PV = nRT
But is that all that is of importance that we can learn without
thermodynamics? NO.
We will show (next slide) that
U = U(T) (ideal gas only),
and U is not a function of V or P
1. We know from quantum mechanics and Boltzmann statistics that
the internal energy of structureless (rare gas) atoms is 3RT
2

2. We know from Quantum Mechanics that the energies of different

degrees of freedom of noninteracting particles add
3. We know that the translational (P.I.B.) degree rigorously does not
interact with internal degrees of freedom
4. Since these other degrees do not depend on translation, they do not
depend on P or V, but rather T alone
5. Therefore
U = U(T) (ideal gas only)
and U of in ideal gas is not a function of V or P
 Your text illustrates the fact that q and w are
not state functions by a series of calculations
on various paths for reversible processes on
ideal gases.
We can get from A to C either directly or as
B+C or D+E.

1. A is a reversible isothermal (constant T) expansion

2. B is a reversible adiabatic (q = 0) expansion
3. C is a reversible constant volume heating
4. D is a reversible isobaric (constant P) expansion
5. E is a reversible constant volume cooling

Process A defines P2 and V2, which we then use to calculate T3 and P3 on the
other two paths.
 A is a reversible isothermal (constant T) expansion
1. Because T constant, ideal gas, UA is constant
2. Because P and V are known at start and finish,
calculate wA, get qA from 1st Law

V2 V2 V2 nRT V2
wrev = − ∫ Pext dV = − ∫ PdV = − ∫ dV = −nRT ln
V1 V1 V1 V V1
∆U A = 0 = q + w
V2
q A = − wA = nRT1 ln
V1
PV
P2 = 1 1
V2
 B is a reversible adiabatic (q = 0) expansion
1. Because P3 < P2 and final volume is same as for
process A, we know T2 < T1
2. Because qB = 0, dU = dw
3. Because U is function only of T for ideal gas,
dU = Cv dT (introducing, of course, a property
of the gas)
nRT
CV dT = − Pext dV = − PdV = − dV
V
reversible Ideal gas
T2 CV V2 V2
∫
T1 R
d ln T = − ∫ d ln V = − ln
V1 V1 For a monatomic gas Cv = 3nR/2 so
3/2
3 T2 V1  T2  V1 and using ideal gas law to eliminate
ln = ln or   = the Vs
2 T1 V2  T1  V2
5/2
P3  T2 
=  and of course wB = ∆U B = CV ∆T = CV (T2 − T1 )
P1  T1 
 C is a reversible constant volume compression
(goes up) and assuming a a rare gas
1. Because U of an ideal gas depends only on T
∆U C = CV ∆T = CV (T1 − T2 ) = 32 nR (T1 − T2 )
2. Because wC = 0, ∆UC = qC

Note that we knew that the two values of T we needed because we completed
a cycle, B+C, starting at upper left, ending up at the same place as A. This
use of cycles is very common, and worked because U is a state function.
 D is a reversible isobaric (constant pressure)
expansion ( that increases both T and V)
and assuming an ideal rare gas
1. Because U of an ideal gas depends only on T
∆U D = CV ∆T = CV (T3 − T1 ) = 32 nR(T3 − T1 )

P1V2
T3 =
nR

w D = − P1 (V2 − V1 ) = −nR(T3 − T1 )
∆U D = 32 R(T3 − T1 ) = q D + w D = q D − nR(T3 − T1 )
q D = 52 nR(T3 − T1 ) = 52 P1 (V2 − V1 )
E is a reversible constant volume expansion (goes down)
1. Because U of an ideal gas depends only on T
∆U E = CV ∆T = CV (T1 − T3 ) = 32 nR(T1 − T3 )
2. Because wE = 0, ∆UE = qE

Because PV=nRT, we know that T3 > T1 > T2 ,

and we know T3 because we are completing a cycle and already knew
∆UA and ∆UD
Assembling it all into a table, for a rare gas, as a function of T1 and T2

q w ∆U
A 3 T2 3 T2 0
− nRT1 ln nRT1 ln
2 T1 2 T1
B 0 3
2 nR (T2 − T1 ) 3
2 nR (T2 − T1 )

C − 32 nR (T2 − T1 ) 0 − 32 nR (T2 − T1 )

B+C − 32 nR (T2 − T1 ) 3
2 nR (T2 − T1 ) 0

D    32     32     32 
nRT1   1  − 1 − nRT1   1  − 1 nRT1   1  − 1
5 T T 3 T
2   T2     T2   2   T2  
     
E   32  0   32 
− nRT1   1  − 1 − nRT1   1  − 1
3 T 3 T
2   T2   2   T2  
   
D+E    32     32  0
nRT1   1  − 1 − nRT1   1  − 1
T T
  T2     T2  
   
Last edited 8:50 AM Jan 11, 2010