Introduction to Thermodynamics

- Laws
- First Law of Thermodynamics (closed
system)
- Differentials and State Functions
- Paths of PV Work
 Definitions

System:
Part of the universe we are interested in. (SYSTEM MUST BE LARGE relative to molecular dimension)

Surrounding: Everything else

Boundary: Separate System and Surrounding

Universe: System + Surrounding

Types of Systems

1. Open
2. Closed
3. Isolated
Properties of the System:
Measurable macroscopic quantities characteristic of the system. (at EQUAILIBRIUM)

Types of Properties :
1. Intensive (Mass independent) : Temperature, Pressure, density etc
2. Extensive (Mass dependent): Mass, Volume, number of particles etc

EQUILIBRIUM:
Macroscopic property not changing

Temperature NOT DEFINED P i

GAS GAS
(state “i”) You are no longer in (state “f”)
f
the PV plot
• Fixed Temp (T) and
V
Pressure (P) • New Temp (T’) and
pressure (P’)
THE STATE OF THERMODYNAMIC EQUILIBRIUM:

When properties of the system remain fixed over time, the system is said to be at “Thermodynamic equilibrium”.

Thermodynamic equilibrium involves three kinds of equilibrium:

1. Mechanical equilibrium:
Pressure of the system (P) is uniform and is equal to the surrounding. Pressure of the system determine “P”
determines the equilibrium.

2. Thermal equilibrium:
Temperature of the system (T) is uniform and is equal to the surrounding. Temperature of the system determine “T”
determines the equilibrium.

3. Chemical equilibrium:
Composition of the system is uniform and does not change over time. Thus, for pure system the equation of chemical
equilibrium does not arise.
 Laws of Thermodynamics

1. Zeroth Law: Ta= Tb, Tb=Tc then Ta=Tc .

Define Thermal equilibrium and provide means of measuring temperature.

2. First Law: Energy can have different forms but the total energy is conserved.
Energy conservation and define internal energy.

3. Second Law: Introduce entropy and explain directional of a process.

4. Third Law: The entropy of a perfect crystal is zero when the temperature of the
crystal is equal to absolute zero (0K). Define absolute zero of “entropy”.
What First Law can address:

Whether a gas will cool upon expansion ?

Calculate the energy changes for chemical reactions.

How much heat will be released from a chemical reaction.

 First Law of Thermodynamics

Conservation of energy: Energy can not be created or destroyed, but can change its form.

Internal Energy Work (w)

U = KE + PE
Heat (q)

𝜟U = q + w
State Function Path Function
Energy change can produce heat and work
 State Functions
A state function is a property that depends only upon the state
of the system. That is, it is independent of how the system was
brought to that state (independent of the path).

A key property of a state function is that its differential can be

integrated in a normal, path independent way.
Energy is a state function:
2 Energy is independent of the path
∫1
dU = U 2 − U1 = ΔU from 1 to 2; it depends only on the
initial (1) and final (2) states.

Work and heat are not state functions.

€ 2 We’ve already seen that work depends
w = − ∫1 Pext dV on the path from state 1 to state 2
(different Pext lead to different w)

€
 Different Differentials
Since work depends upon how a process is carried out, work
is not a state function, work is a path function, so we write,
2
∫1
δw = w (not Δw or w 2 − w1)
An inexact Cannot be integrated in the
differential normal way

€
Energy is a state function, and dU is an exact differential.

State functions: Path functions:

2 2
∫1
dU = U 2 − U1 = ΔU ∫ 1
δq = q (not Δq or q2 − q1)
2
∫1
δw = w (not Δw or w 2 − w1)
€ €

€
 The First Law of Thermodynamics
Energy is conserved

dU = δq + δw (differential form)

ΔU = q + w (integral form)

Even though δq and δw are path functions (inexact differentials),

their sum is a state function (an exact differential).
 CLOSE SYSTEM ∆U = q + w (First Law)

∆U = q + ( wMech +wnon-Mech )
F
LETS NOT WORRY ABOUT Wnon-Mech

wMech = Force x displacement

h
=Fxh
A =area
= (F/A) x (Ax h)
= P x ∆V
V1 V2 Change in volume
Mechanical Work
(wMech)
∆U= U2 –U1 = q – P ∆V
Sign Convention: q
q
w V2
w Mechanical (PV) Work: w = – ∫ P dV
V1
ALWAYS THINK ABOUT SIGN OF ∆U
Other type of works
 Thermometer Heat ?
q
water hot Q∝ ∆T ∆T = temperature change
mw = Mass of water (gms)
∝ mw ∆T C = Specific heat (property
of material)
= C mw ∆T
For water, C = 1 cal/(gm 0C)

Now one can find “C” for other material (say Iron)
Apply 1st Law,
Energy conservation
Iron ∑Q=0
(Temp =T2)
Water =) 1. mw. (Tf-T1)+ CFe. mFe. (Tf-T2) = 0
(Temp =T1)
I know mw, Tf, T1, T2
Final
(Temp =Tf)
Application
History: Heat

"An Experimental Enquiry Concerning the Source of

the Heat which is Excited by Friction",
(1798), Philosophical Transactions of the Royal
Society p. 102.
 History: Heat
Q = 1. mw ∆T
= Mgh -KE
(mechanical energy)

h
M

James Prescott Joule

Mechanical equivalent of heat (1841)

 Understanding “Heat” require the knowledge:
Everything is made up of atoms

Colliding car

K.E goes into Kinetic Energy

atoms = Heat of the box ≠ heat (q)

Atomic motion

“q”
Next: Paths of PV work