CHE121-1P

Prepared by:
Rhoda B. Leron

First Law of
Thermodynamics
First law of thermodynamics

Joule experiment A quantitative relationship exists

between work and heat !!!

Findings:
•  For each fluid, a fixed
amount of work was
required per unit mass
for every degree of
temperature rise
caused by stirring.

•  The original
temperature of the fluid
can be restored by the
transfer of heat through
simple contact with a
cooler object.

CHE Thermodynamics 1
First law of thermodynamics

Internal energy

W Q
U

Question: Where is this energy between its addition to

and transfer from the fluid?

CHE Thermodynamics 1
First law of thermodynamics

Internal energy
•  Refers to energy of the molecules internal to a substance
•  Kinetic energy of translation, rotation and internal
vibration
•  Potential energy resulting from intermolecular forces
•  Does not include energy due macroscopic position or
movement
•  A thermodynamic primitive (has no concise definition)
•  Cannot be directly measured (absolute values are
unknown)
•  Changes in internal energy are quantified.

CHE Thermodynamics 1
First law of thermodynamics

Statement:

Although energy assumes many forms, the total quantity

of energy is constant, and when energy disappears in one
form it appears in another form.

As a consequence, this law states that the energy of the

thermodynamic universe is constant.

Δ(Energy of the system) + Δ(Energy of surroundings) = 0

CHE Thermodynamics 1
First law of thermodynamics

Notes:
•  Q and W represent energy in transit across
the boundary.
•  Q and W are never stored or contained in
the system.
•  PE, KE, and U reside with and stored
with matter.

CHE Thermodynamics 1
Basic concepts

Recall:

For a closed system:

Δ(Energy of the system) = Q + W

ΔUt =Q + W

dUt =dQ + dW

where Ut – total internal energy of the system (extensive

property)
CHE Thermodynamics 1
Basic concepts

For a closed system:

Δ(nU) = nΔU = Q + W

d(nU) = ndU = Q + W

For n = 1

ΔU = Q + W dU = dQ + dW

where U – specific internal energy (intensive property)

CHE Thermodynamics 1
Basic concepts

Constant-volume process

d(nU) = dQ – Pd(nV)

d(nU) = dQ + dW

For a constant n, constant V process è W = 0

d(nU) = dQ

Q = nΔU
CHE Thermodynamics 1
Basic concepts

Constant-pressure process

dQ = d(nU) + Pd(nV)

For a constant n, constant P process

dQ = d(nU) + d(nPV)

dQ = d[n(U + PV)]
By definition:

H ≅ U + PV Q =ΔnH
CHE Thermodynamics 1
Basic concepts

Heat capacity
dQ
C≡
dT

At constant V

dQ = dU
# ∂U &
CV ≡ % (
$ ∂T 'V
CHE Thermodynamics 1
Basic concepts

For a constant-V in a closed system

dU = CV dT
T2
ΔU = ∫ T1
CV dT

For a mechanically reversible constant-V process

T2
Q = nΔU = n ∫ CV dT
T1
CHE Thermodynamics 1
Basic concepts

Heat capacity

At constant P

dQ = d(nH )
# ∂H &
CP ≡ % (
$ ∂T 'P

CHE Thermodynamics 1
Basic concepts

For a constant-P, closed system

dH = CP dT
T2
ΔH = ∫ T1
CP dT

For a mechanically reversible constant-P process

T2
Q = nΔH = n ∫ CP dT
T1
CHE Thermodynamics 1
Basic concepts

Only for mechanically reversible constant-P process

that:

T2
Q = nΔH Q = n ∫ CP dT
T1

W = −PnΔV

CHE Thermodynamics 1
Mass and energy balances for open systems

Mass balance for open systems

Control volume – the region of space identified for analysis of
open systems

CHE Thermodynamics 1
Mass and energy balances for open systems

Continuity equation:
Mass balance:

dmCV •
+ Δ(m ) fs = 0
dt
• • •
Δ(m ) fs = m out − m in
In terms of u, ρ, A

dmCV
+ Δ(uρ A) fs = 0
dt
rate of accumulation
CHE Thermodynamics 1
Mass and energy balances for open systems
Continuity equation:
At steady state: No accumulation

dmCV
 fs = 0
+ Δ(m)
dt
 fs = 0
Δ(m)

When there is but one entrance and one exit streams:

u1ρ1 A1 = u2 ρ2 A2
Mass flow rate
u1 A1 u2 A2 uA is constant.
m = = =
V1 V2 V
CHE Thermodynamics 1
Mass and energy balances for open systems
General energy balance:

! u2 $
Each stream transports energy at the rate: m #U + + zg &
" 2 CHE%Thermodynamics 1
Mass and energy balances for open systems

Energy balance:

d(mU)CV )# u2 &• ,
= −Δ +%U + + zg ( m fs . + Q + workrate
dt *$ 2 ' -

Including all forms of work:

d(mU)CV )# u2 &• , •
= −Δ +%U + + zg ( m fs . + Q − Δ[( PV ) m] fs + W
dt *$ 2 ' -

CHE Thermodynamics 1
Mass and energy balances for open systems

Energy balance:

d(mU)CV )# u2 &• ,
= −Δ +% H + + zg ( m fs . + Q + W
dt *$ 2 ' -

d(mU)CV (" u2 %• +
+ Δ *$ H + + zg ' m fs - = Q + W
dt )# 2 & ,

CHE Thermodynamics 1
Simplifying conditions

CHE Thermodynamics 1
Steady state open system

Ws (+) Ws (-)
Q (-)
Q (+)

system Outlet (2)

u2
z2

Inlet (1)
u1
z1
Reference or datum level

CHE Thermodynamics 1
Steady state open system

Energy balance:

ΔH + ΔEK + ΔEP = Q + W

Δu 2 u 22 − u12
where ΔE K = =
2 2
ΔE p = gΔz = g (z 2 − z1 )
ΔH = H 2 − H1
Q is positive (+) when energy is added to the system and negative (-) when energy is
released from the system
Ws is positive (+) when work is consumed by the system or supplied to the system (eg.
compressor, blower, fan) and negative (-) if work is produced by the system (eg.
turbine)

CHE Thermodynamics 1
Closed system

0
d(mU)CV •
+ Δ(H m) fs = Q + W
dt

ΔU = Q + W
CHE Thermodynamics 1
Closed system

ΔU = Q + W

where ΔU = U 2 − U1
W = −∫ pdV
Q is positive (+) when energy is added to the system and negative (-) when energy is
released from the system
W is positive (+) if work is done on the system and negative (-) when work is done by
the system

CHE Thermodynamics 1
Isolated system

v Mass is invariant

v Energy is invariant

v ΔU=0

CHE Thermodynamics 1
Review definitions
Enthalpy H ≡ U + PV
Gibbs Free Energy G ≡ H − TS
Helmholtz Free Energy A ≡ U − TS
Constant-volume heat capacity ⎛ ∂U ⎞
CV = ⎜ ⎟
⎝ ∂T ⎠V
Constant-pressure heat capacity ⎛ ∂H ⎞ Always true
C P = ⎜ ⎟ regardless
⎝ ∂T ⎠ P of nature of
Coefficient of thermal expansion 1 ⎛ ∂V ⎞ the system!
α = ⎜ ⎟
V ⎝ ∂T ⎠ P
Isothermal compressibility 1 ⎛ ∂V ⎞
κ T = − ⎜ ⎟
V ⎝ ∂P ⎠T
Joule-Thomson coefficient ⎡ ⎛ ∂V ⎞ ⎤
⎢V − T ⎜ ⎟ ⎥
⎣ ⎝ ∂T ⎠ P ⎦
µ=−
CP
CHE Thermodynamics 1
 Thermodynamic Processes of
an Ideal Gas in a Closed System
PVT
Process Characteristic Relationship ΔH ΔU Q W

V2 V2
Isothermal T=constant PV=constant 0 0 RT ln − RT ln
V1 V1
T2
∫ C p dT
Isobaric P=constant V/T=constant T1 T2
ΔH − PΔV
or ∫ CV dT
T1
ΔU + PΔV
Isochoric T2
∫ C p dT
or V=constant P/T=constant T1 T2
ΔU 0
∫ CV dT
Isometric or T1
Δ U + VΔ P
RΔT
Adiabatic Q=0 TV γ −1
= cons tan t T2 T2 0 γ −1
∫ C p dT ∫ CV dT
T1 T1

1−γ
P2V2 − P1V1
TP γ
= cons tan t
γ −1
PV γ = cons tan t ⎡ γ −1
⎤
RT1 ⎢⎛ P2 ⎞ γ
⎜ ⎟ − 1⎥
γ − 1 ⎢⎜⎝ P1 ⎟⎠ ⎥
⎣⎢ ⎦⎥

CHE Thermodynamics 1
Sample Problems
Ideal gas closed system

An ideal gas initially at 600 K and 10 bar undergoes a four-step

mechanically reversible cycle in a closed system. In step 1-2,
pressure decreases isothermally to 3 bar; in step 2-3, pressure
decreases at constant volume to 2 bar; in step 3-4, volume
decreases at constant pressure; and in step 4-1, the gas returns
adiabatically to its initial state. Take CP = (7/2) R and CV = (5/2)
R.
a.  Sketch the cycle on a PV diagram.
b.  Determine (where unknown) both T and P for states 1, 2, 3, and 4.
c.  Calculate Q, W, ΔU, and ΔH for each step of the cycle.
d.  Calculate W for the process.

CHE Thermodynamics 1
Sample Problems
Steady-state open system

1.  Air at 600 kPa and 500 K enters an adiabatic nozzle that has
an inlet-to-exit area ratio of 2:1 with a velocity of 120 m/s
and leaves with a velocity of 380 m/s. Determine
a.  The exit temperature
b.  The exit pressure of air

2.  A hot-water stream at 80°C enters a mixing chamber with a

mass flow rate of 0.5 kg/s where it is mixed with a stream of
cold water at 20°C. If it is desired that the mixture leave the
chamber at 42°C, determine the mass flow rate of the cold-
water stream. Assume all the streams are a pressure of 250
kPa and the change in the kinetic energy of the system is
negligible. CHE Thermodynamics 1
Sample Problems
Unsteady-state open system

CHE Thermodynamics 1
Sample Problems
Unsteady-state open system

1.  A rigid, insulated tank that is initially evacuated is connected

through a valve to a supply line that carries steam at 4 MPa. Now
the valve is opened, and steam is allowed to flow into the tank
until the pressure reaches 4 MPa, at which the valve is closed. If
the final temperature of the steam in the tank is 550°C, determine
the temperature of the steam in the supply line and the flow work
per unit mass of the steam.

2.  A 0.3-m3 rigid tank is filled with saturated liquid water at 200°C.
A valve at the bottom of the tank is opened, and liquid is
withdrawn from the tank. Heat is transferred to the water such that
the temperature in the tank remains constant. Determine the
amount of heat that must be transferred by the time one-half of the
total mass has been withdrawn. CHE Thermodynamics 1
Introduction to Thermodynamics