First Law of Thermodynamics o Δ (Energy of the system) + Δ

(Energy of surroundings) = 0
I. Joule’s Experiment and Internal Energy  Heat and work: energy flows to or from a
II. First Law of Thermodynamics system
a. Equations of Energy
 Potential, kinetic, and internal energy:
III. Closed System or Isolated System
a. Closed System
quantities of energy associated with a
b. Equilibrium system
c. Reversible Process
d. Isolated System  “expression of the conservation of energy
e. Thermodynamics of Ideal Gas in Closed Systems principle, and it asserts that energy is a
IV. Open System thermodynamic property”
a. Mass Balance
b. Energy Balance
c. Energy Balance for Steady State Flow Processes
 CLASSIFICATION OF SYSTEM
o Open System – matter crosses the
I. Joule’s Experiment and Internal Energy
system boundary as streams that enter
ღ Joule’s Experiment
or leaves the process
- James Prescott Joule
o Closed System - does not permit
- Mechanical work done is equivalent to
transfer of matter between system and
heat produced
surrounding
W = JQ
 Energy transport appears as
heat or work
 No energy transport
associated with matter
o Isolated System - no transfer of matter,
heat and work

- Cylindrical calorimeter made of copper III. Closed and Isolated System

was covered with water tight lid ღ Energy Balance for Closed Systems
- By rotating the handle, masses were Δ(Energy of surroundings) = ±Q ± W
raised through a height ‘h’; in reverse Δ(Energy of surroundings) = Qsurr + Wsurr = − Q − W
direction the weight fall down in the
same height  +Q (heat absorbed) ; +W(done to the
- Mechanical work was converted to heat system)
and the temperature increased  −Q (heat released) ; −W(done by the
- 4.186 kJ/cal mechanical energy was lost system)
as the temperature of 1kg of water
increased by 1C Δ(Energy of System) = Q + W

ღ Internal Energy  Sign Conventions:

- Energy of molecules comprising the ΔU = Q – W : heat in, work out
substance ΔU = Q + W : heat in, work in
- Addition of heat increase molecular
activity, increase internal energy  undergo processes during which only the
- Internal Energy = Etranslation + Evibration + internal energy of the system changes.
Erotation + PE ΔUt = Q + W
finite change in internal energy
II. First Law of Thermodynamics
ღ First Law dUt = dQ + dW
 Although energy assumes many forms, the differential change in internal energy
total quantity of energy is constant, and  for homogeneous system:
when energy disappears in one form it Vt = mV Vt = nV
appears simultaneously in other forms. Ut = mU Ut = nU
 - Vt and Ut are extensive; specific and
molar volume V and specific and molar
internal energy U are intensive
Example 1  For a closed system undergoing the same
Water flows over a waterfall 100m in change in state by several processes,
height. Take 1kg of the water as the system, and experiment shows that the amounts of heat
assume that it does not exchange energy with its and work required differ for different
surroundings. processes, but that the sum Q + W is the
(a) What is the potential energy of the water at the same for all processes.
top of the falls with respect to the base of the falls?
(b) What is the kinetic energy of the water just Example 2.3
before it strikes bottom? A gas is confined in a cylinder by a piston.
(c) After the 1kg of water enters the stream below The initial pressure of the gas is 7 bar, and the
the falls, what change has occurred in its state? volume is 0.10 m3. The piston is held in place by
latches.
The 1 kg of water changes energy with the (a) The whole apparatus is placed in a total vacuum.
surroundings, thus, What is the energy change of the apparatus if the
ΔEsystem = ΔU + ΔKE + ΔPE = 0 restraining latches are removed so that the gas
suddenly expands to double its initial volume, the
(a) Potential Energy @ top of falls piston striking other latches at the end of the
PE1 = mzg = (1 kg)(100 m)(9.81 m/s 2) process?
PE1 = 981 J (b) The process described in (a) is repeated, but in
air at 101.3 kPa, rather than in a vacuum. What is
(b) Kinetic Energy just before it strikes the bottom the energy change of the apparatus? Assume the
ΔU + ΔKE + ΔPE = 0 rate of heat exchange between the apparatus and
ΔU + KE2 – KE1 + PE2 – PE1 = 0 the surrounding air is slow compared with the rate
* During free fall of water, no mechanism exists for at which the process occurs.
conversion of PE and KE into internal energy
ΔU = KE1 = PE2 = 0 (a) Q= 0, W=0, ΔU = 0
*PE2 – baba ng stream, KE1 – top ng stream (b)
KE2 = PE1 = 981 J Q=0 Pex = 101.3 kPa
V1 = 0.10 m3 V2 = 0.20 m3
(c) change
ΔEsystem = ΔU + ΔKE + ΔPE = 0 W = -PexdV
ΔPE = 0 W = -101.3 kPa (0.20-0.10) m3
ΔU + ΔKE = ΔU + KE3 – KE2 W = -10.13 kJ
KE3 = 0 (nasa stream na, negligible)
ΔU = KE2 = 981 J ΔU = Q + W = 0 -10.13 kJ
ΔU = -10.13 kJ
* no change in T, assuming T falls is almost the same
as Tstream Example 2.4
When a system is taken from state a to state b in
ღ Equilibrium and the Thermodynamic State the accompanying figure along path acb, 100 J of
 Equilibrium – absence of any tendency heat flows into the system and the system does 40 J
toward changes on a macroscopic scale of work.
 State Functions – do not depend on the
past history of the substance nor on the
means of which it reaches a given state

 Path Functions – account for energy

changes occur in the surrounding
 return to their original condition once the
process is initiated
 Usually calculated by a two-step procedure
 To find the work of an irreversible process
for the same change in V t needs efficiency
which relates the actual work to the
reversible work
 Examples:
o Relative motion with friction
o Throttling
o Heat transfer
(a) How much heat flows into the system along path o Diffusion
aeb if the work done by the system is 20 J? o Electricity flow through a resistance
(b) The system returns from b to a along path bda. ღ Reversible Process
If the work done on the system is 30 J, does the  Can be reversed at any point by an
system absorb or liberate heat? How much? infinitesimal change in external conditions
 Is never more than minutely removed from
ΔUab = Qacb + Wacb = 100 + (-40) = 60 J equilibrium
(a)  Traverses a succession of equilibrium states
ΔUab = Qaeb + Waeb  Is frictionless
60 J = Qaeb – 20 J  Is driven by forces whose imbalance is
Qaeb = 80 J infinitesimal in magnitude
(b)  Proceeds infinitely slowly/gradually
ΔUab = Qbda + Wbda  When reversed, retraces its path, restoring
60 J = Qbda + 30 J the initial state of system and surroundings
Qbda = -90 J ; liberate/released
 Computing Work for Reversible Process
ღ Reversible Process  Work of compression or expansion of a gas
 when its direction can caused by the displacement of a piston in a
be reversed at any cylinder:
point by an dW = -PdVt
infinitesimal change in  If (a) the system is no more than
external conditions. infinitesimally displaced from a state of
 yields the minimum internal equilibrium, characterized by
work input required or maximum work uniformity of temperature and pressure (b)
output attainable from a specified process the system be no more than infinitesimally
(idealized cases of real processes) displaced from mechanical equilibrium with
 Examples: its surroundings, it is said to be
o extension of springs mechanically reversible,
o slow adiabatic compression or
expansion of gases electrolysis
(with no resistance in the
electrolyte)
 Enthalpy for Closed System, Reversible
o the frictionless motion of solids
Process
o slow isothermal compression or
dU = dQ + dW
expansion of gases
if dW = -PdV : dU = dQ - PdV
constant volume (V) : dU = dQ
ღ Irreversible Process
ΔU = Q (constant V)
 process in which the
mathematical (and only) definition of
system and the
enthalpy is: H ≡ U + PV ; ΔH = ΔU + Δ(PV)
surroundings do not
constant pressure (P) : dH = dQ
ΔH = Q (constant P)
 Given:
 Heat Capacity P1 = 14 bar, V1 = 0.03 m3, V2 = 0.06 m3
constant volume (W = 0) PV = K
Required: W
W = -PdV ; PV = K –> K/V =P
constant pressure (W = -PdV) −K
W= dV (Integrate)
V
dV V2 V2
W =−K ¿−K ln ¿−P1 V 1 ln
V V1 V1
*For solid and liquid: Cp = Cv
(Can use isothermal eq)
W =−¿
W = -29 112.18 J

ღ Adiabatic Process
 Adiabatic Process - no heat is gained or lost
ღ Polytropic Process
by the system (Q=0); all the change in
 Polytropic Process - (turning many ways) is
internal energy is in the form of work done
any thermodynamic process that can be
 Adiabatic Expansion: dV>0, dT<0,
expressed by the following equation:
temperature drops
 Adiabatic Compression: dV<0, dT>0,
temperature rises

Example 2.5
A horizontal piston/cylinder arrangement is placed
in a constant-temperature bath. The piston slides in
the cylinder with negligible friction, and an external
force holds it in place against an initial gas pressure Example 2.6
of 14 bar. The initial gas volume is 0.03 m 3. The Calculate ΔU and ΔH for 1 kg of water when it is
external force on the piston is reduced gradually, vaporized at the constant temperature of 100°C
and the gas expands isothermally as its volume and the constant pressure of 101.33 kPa. The
doubles. If the volume of the gas is related to its specific volumes of liquid and vapor water at these
pressure so that PVt is constant(K), what is the work conditions are 0.00104 and 1.673 m3·kg−1,
done by the gas in moving the external force? respectively. For this change, heat in the amount of
REVERSIBLE 2256.9 kJ is added to the water.
 a*Heating at constant V, tataas from P 1V2Ta, change
to T2, change P
b*Heating at constant V, from P1V1T1 upwards,
intermediate T, change in P
b*Cooling at constant P, change in V, change to T 2

P1V1 = P2V2
At Constant Temperature: ΔU = 0, ΔH=0
(1 bar)(0.02479 m3·mol−1) = (3 bar)V2
At Constant Pressure:
V2 = 0.008263 m3
Q = ΔH = 2256.9 kJ
ΔH = ΔU + Δ(PV) -> ΔU + PΔV
P1 = 1 bar
ΔU = ΔH – PΔV
V1 = 0.02479 m3·mol−1
ΔU = 2256.9 kJ – (101.33kPa)(1.673-
P2 = 3 bar
0.00104) m3
V2 = 0.008263 m3
ΔU = 2087.48 kJ
T1 = T2 = 298.15 K

@a1: cooling at constant P

Example 2.7
P1 = 1 bar = P2
Air at 1 bar and 298.15 K is compressed to 3 bar and
V1 = 0.02479 m3·mol−1
298.15 K by two different closed-system
V2 = 0.008263 m3
mechanically reversible processes:
T1 = T2 = 298.15 K
(a) Cooling at constant pressure followed by heating
CP = 29.100 J· mol−1·K−1
at constant volume.
(b) Heating at constant volume followed by cooling
V 1 V 2 0. 02479 0.008263
at constant pressure. = = =
Calculate the heat and work requirements and ΔU
T 1 T a 298.15 Ta
and ΔH of the air for each path. The following heat Ta = 99.38 K
capacities for air may be assumed independent of
temperature: Q = ∆H = Cp∆T = Cp (Ta-T1)
CV = 20.785 and CP = 29.100 J· mol−1·K−1 Q = ∆H = 29.100 J· mol−1·K−1(99.38 –
Assume also that air remains a gas for which PV/T is 298.15)K
a constant, regardless of the changes it undergoes. Q = -5784.23 J
At 298.15 K and 1 bar the molar volume of air is
0.02479 m3·mol−1. ∆U = ∆H – P∆V
∆U = (-5784.23 J) – (1x105 Pa)( 0.008263 m3
(a) P1 = 1 bar - 0.02479 m3·mol−1)
V1 = 0.02479 m3·mol−1 ∆U = -4131.53 J
P2 = 3 bar
T1 = T2 = 298.15 K W = -P∆V = – (1x105 Pa)( 0.008263 m3 -
(bumalik ang system from initial state to 0.02479 m3·mol−1)
final state) W = 1652.7 J

@a2: heating at constant V

CV = 20.785 J· mol−1·K−1
Ta = 99.38 K

Q = ∆U = CV∆T = 20.785 J· mol−1·K−1(298.15 –

99.38)K
Q = ∆U = 4143.43 J

a*Since cooling at constant P, plot horizontally, ∆H = ∆U + V∆P

intermediate T, magcchange V
 ∆H = 4143.43 J + (0.008263)[(3-1)x105] Calculate the internal energy and enthalpy changes
∆H = 5784.03 J resulting if air changes from an initial state of 5°C
and 10 bar, where its molar volume is 2.312×10 −3
W=0 m3·mol−1, to a final state of 60°C and 1 bar. Assume
also that air remains a gas for which PV/T is
@a: overall process constant and that CV = 20.785 and CP = 29.100
Q = -5784.23 J + 4143.43 J = -1652.8 J J·mol−1·K−1.
W = 1652.7 J + 0 = 1652.7 J
∆H = -5784.23 J + 5784.03 J = 0 Example 3.4
∆U = -4131.53 J + 4143.43 J = 0 A gas in its ideal-gas state undergoes the following
sequence of mechanically reversible processes in a
@b1: heating at constant V closed system:
CV = 20.785 J· mol−1·K−1 (a) From an initial state of 70°C and 1 bar, it is
compressed adiabatically to 150°C.
P 1 P2 ¯ ¯ (b) It is then cooled from 150 to 70°C at constant
= =1 ¿ =3 ¿ ¿¿ pressure.
T1 T b 298.15 Ta
Tb = 894.45 K (c) Finally, it expands isothermally to its original
state.
Q = ∆U = CV∆T = 20.785 J· mol−1·K−1(894.45- Calculate W, Q, ΔUig, and ΔHig for each of the three
298.15)K processes and for the entire cycle. Take C Vig =
Q = ∆U = 12394.10 J 12.471 and CPig = 20.785 J· mol−1·K −1

∆H = ∆U + V∆P
∆H = 12394.10 J + (0.02479)[(3-1)x105]
∆H = 17352.1 J IV. Open System
ღ Mass and Energy Balances for Open Systems
W=0J  Measures of Flow
o mass flow rate¿
@b2: cooling at constant P ṁ=M ṅ=uAρ
CP = 29.100 J· mol−1·K−1 o molar flow rate ( ṅ )
ṅ=uAρ
Q = ∆H = Cp∆T o volumetric flow rate ( q )
Q = ∆H = 29.100 J· mol−1·K−1(298.15 – q = uA
894.45)K o velocity(u)
Q = -17352.33 J
Example
∆U = ∆H – P∆V Liquid n-hexane flows at a rate of m = 0.75 kg/s in a
∆U = (-17352.33 J) – (3x105 Pa)( 0.008263 pipe with inside diameter D = 5cm. What are q, n ,
m3 - 0.02479 m3·mol−1) and u? What would these quantities be for the
∆U = -12394.23 J same m if D = 2cm? Assume for liquid n-hexane that
ρ=659 kg/m3.
W = -P∆V = -(3x105 Pa)( 0.008263 m3 -
0.02479 m3·mol−1)  Mass Balance for Open Systems
W = 4958.1 J

@b: overall process

Q = 12394.10 J + -17352.33 J = -4958.23 J
W = 0 J + 4958.1 J = 4958.1 J
∆H = 17352.1 J + -17352.33 J = 0
∆U = 12394.10 J + -12394.23 J = 0

Example 2.8
 Control Volume - region of space identified
for analysis of open systems
 Control Surface – separates control volume
from its surroundings

 control volume

 continuity equation:

 steady-state flow process:

 Thus,

 General Energy Balance

 Energy Balances for Steady-State Flow

Processes
Since

Then

For control volume with 1 entrnace and 1

exits, and dividing the m,

If KE and PE is neglible,
 Flow Calorimeter for Enthalpy
Measurements