K1: TERMODINAMIKA DASAR -

PENDAHULUAN
AUGUST 16, 2019
Thermodynamics and laws of thermodynamics

Thermodynamics
heat motion
 Describes macroscopic properties of equilibrium systems
 Entirely empirical
 Summarized in 4 Laws

 Zeroth law -> Defines temperature (T)

 First law -> Defines energy (U)
 Second law -> Defines entropy (S)
 Third law -> Gives numerical value to entropy

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Definition

• System: The part of the Universe that we choose to study

• Surroundings: The rest of the Universe
• Boundary: The surface dividing the System from the Surroundings
Note: Boundary can be an imaginary one!

Systems can be:

• Open: Mass and Energy can transfer between the System and the
Surroundings
• Closed: Energy can transfer between the System and the Surroundings, but
NOT mass
• Isolated: Neither Mass nor Energy can transfer between the System and the
Surroundings 3
Definition

Two classes of properties

• Extensive: Depend on the size of the system (n, m, V,…)
• Intensive: Independent of the size of the system (T, p, V/n, …)

The State of a System at Equilibrium:

• Defined by the collection of all macroscopic properties that are described by
State variables (p, n, T, V,…)
[State variables are INDEPENDENT of the history of the system]
• For a one-component System, all that is required is “n” and 2 variables. All
other properties then follow.
e.g., V = f (n, p,T)
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Definition

Notation:
• 3 H2 (g, 1 bar, 100 °C)

Change of state:
3 H2 (g, 5 bar, 100 °C) -> 3 H2 (g, 1 bar, 50 °C)

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Definition

Path: Sequence of intermediate states

Process: Describes the Path

• Reversible (always in Equilibrium)
• Irreversible (defines direction of time)
• Adiabatic (no heat transfer between system and surroundings)
• Isobaric (constant pressure)
• Isothermal (constant temperature)
• Constant Volume
• ….
• …. 6
Thermal equilibrium

A + B A B A B
HOT COLD Warm
Heat flows

WARM
Zeroth Law of Thermodynamics
• If A and B are in thermal equilibrium and B
HOT COLD
• If B and C are in thermal equilibrium
A C
• Then, A and C are in thermal equilibrium

Heat flow? 7
Problem set

• Introduction to chemical engineering thermodynamics - 7th ed. / J.M. Smith,

H.C. Van Ness, M.M. Abbott.
Chapter 1: P1.4, P1.6, P1.8, P1.10, P1.12, P1.14
Due date: August 23, 2019

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Work

Work: w=F.l
Applied force distance
Pexternal
Expansion/Compression work
l Pexternal F= Pext A

Area = A W = -(Pext A)l = -Pext ΔV

Convention: Having a “-“ sign here implies

w >0 if ΔV <0 , that is, positive work
means that the surroundings do work to
Differential form the system. If the system does work on
dW = -Pext dV the surroundings (ΔV >0) then w <0.
WORK depends on the PATH!
2
W = -‫׬‬1 𝑃𝑒𝑥𝑡 𝑑𝑉
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Path dependence of w

Assume a reversible process so that pext = p

H2 (g, p1, V1) -> H2 (g, p2, V2)

Compression: V1 > V2 and P1 < P2

Pext = P1 Two paths:

compression Pext = P2 (1) First, V1 -> V2 at constant P
P1, V1
Then P1 -> P2 at constant V
P2, V2
(2) First P1->P2 at constant V
initial final
Then V1->V2 at constant P

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Path dependence of w

1 2
P P
final final
P2 P2

P1 P1
initial initial

V V
V2 V1 V2 V1
Path dependence of w

𝑉2 𝑉2 𝑉1 𝑉2
𝑊1 = − න 𝑃𝑒𝑥𝑡 𝑑𝑉 + − න 𝑃𝑒𝑥𝑡 𝑑𝑉 𝑊2 = − න 𝑃𝑒𝑥𝑡 𝑑𝑉 + − න 𝑃𝑒𝑥𝑡 𝑑𝑉
𝑉1 𝑉2 𝑉1 𝑉1
0 0
𝑉2 𝑉2 𝑉1 𝑉2
𝑊1 = − න 𝑃1 𝑑𝑉 − න 𝑃 𝑑𝑉 𝑊2 = − න 𝑃𝑑𝑉 − න 𝑃2 𝑑𝑉
𝑉1 𝑣2 𝑉1 𝑣1

𝑊1 = 𝑃1 (𝑉1 − 𝑉2 ) 𝑊2 = 𝑃2 (𝑉1 − 𝑉2 )

(Note w > 0, work done to system to compress it)

W1 ≠ W 2
Note for the closed cycle (W1 - W2 ≠ 0)

W is not a state function -> It depends on the path!

Path dependence of w

1 2
P P
final final
P2 P2

W2
P1 P1
initial initial
W1

V V
V2 V1 V2 V1
Heat

That quantity flowing between the system and the surroundings

that can be used to change the temperature of the
system and/or the surroundings.

Sign convention: If heat enters the system, then it is positive

Heat (q), like w, is a function of path. Not a state function