®

Because learning changes everything.

Chapter 2:
The First Law and Other Basic Concepts

Copyright 2022 © McGraw Hill LLC. All rights reserved. No reproduction or distribution without the prior written consent of McGraw Hill LLC.
 2.1: Joule’s Experiments

• Modern concept of heat developed by James P. Joule (1818-

1889) in the 1840s
• Simple experiments, but done carefully to ensure accuracy
– Known amounts of water, oil, and mercury placed in an insulated
container; fluid agitated with rotating stirrer
– Work on the fluid by the stirrer and corresponding temperature changes
in the fluid were carefully measured

• Found that a fixed amount of work was required per unit mass
of fluid for every degree of temperature rise
• Demonstrated relationship between heat & work
© McGraw Hill LLC 2
 2.2: Internal Energy
• Definition: Internal Energy – energy of molecules internal to a
substance (kinetic energy of translation, rotation, and
vibration of atoms and molecules)
– Does not include energy due to a substance’s macroscopic
position/velocity
– Does include potential energy associated with intermolecular forces

• Addition of heat or work done to substance can increase its

internal energy
• No concise definition; cannot be directly measured – known
as a thermodynamic primitive
– Absolute values of internal energy are unknown, but changes CAN be
measured and are more relevant

© McGraw Hill LLC 3

 2.3: The First Law of Thermodynamics
• Although energy assumes many forms, the total quantity of
energy is constant, and when energy disappears in one form
it appears simultaneously in other forms
• The system is defined as where the process occurs; the
surroundings are everything with which the system interacts

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

(2.1)
• In thermodynamics, heat & work represent energy flows
across the boundary between system and surroundings, not
energy stored in the system
• Potential, kinetic, and internal energy refer to energy
associated with (stored in) the system
© McGraw Hill LLC 4
 2.4: Energy Balance for Closed Systems
• Definitions:
– Closed system: system boundaries do not allow transfer of matter
– Open system: both matter and energy cross system boundaries
– Isolated system: neither matter nor energy cross system boundaries

• For closed systems, because no streams enter or leave, no

energy is associated with material flows across the boundary
• All energy exchange between a closed system and its
surroundings appear as heat and work, and alter the total
internal energy of the system bya an amount of ∆Ut :
∆Ut = Q + W (2.3)
or
dUt = dQ + dW (2.4)
© McGraw Hill LLC 5
 Extensive vs. Intensive Properties
• Definitions:
– Extensive properties: dependent on the quantity of a material
• Ex. total volume (Vt ), total internal energy (Ut )

– Intensive properties: independent on the quantity of a material

• Ex. temperature (T ), pressure (P )

• Dividing an extensive property by its quantity (mass or

moles), yields an intensive property:
– Specific Volume, V = Vt/m; Molar Volume, V = Vt/n
– Specific Internal Energy, U = Ut/m; Molar Internal Energy, U = Ut/n

• Likewise, equations 2.3 and 2.4 can be re-written:

∆(nU) = n∆U = Q + W (2.5) d(nU) = ndU = dQ + dW (2.6)

© McGraw Hill LLC 6
2.5: Equilibrium and the Thermodynamic State
• Equilibrium: A condition reflecting the absence of any net
changes in the state of a system as well as the absence of any
driving force for change
• Examples:
– Mechanical: pressures on both sides of a piston are equal, so there is
no motion of the piston (forces in balance, no pressure driving force)
– Thermal: temperatures of two objects in contact are equal, so there is
no heat flow (no temperature driving force for heat flow)
– Phase: chemical potentials of species in multiple phases are equal, so
no net flow of material between phases (no chemical driving force)
– Chemical: chemical potentials of reactants and products balance, so
the net formation of products ceases (no chemical driving force)

© McGraw Hill LLC 7

 Thermodynamic State and State Functions
• Definitions:
– Thermodynamic Properties: temperature, pressure, molar/specific
volume (or density)
– Thermodynamic State: macroscopic condition of the system, as defined
by T, P, and V (or ρ) at fixed composition
– State Function: property that depends only on the initial and final states,
not the path taken between the states (such as U)
– Path Function: property that does depend on the path taken between
two states (prototypical examples are Q andW )

• Differential state functions represent differential changes

𝑃2 𝑉2
‫𝑃 = 𝑃𝑑 𝑃׬‬2 − 𝑃1 = ∆𝑃 and ‫𝑉 = 𝑉𝑑 𝑉׬‬2 − 𝑉1 = ∆𝑉
1 1

• Differential path functions represent amounts, not changes

‫ ׬‬dQ = Q and ‫ ׬‬dW = W
© McGraw Hill LLC 8
 Representation on a P-V Diagram
• Independent Thermodynamic
Properties = P, Vt
• Thermodynamic State = any
specific (P, V ) pair/point
• State Function = any quantity
dependent only on states 1 and 2
• Thermodynamic Path = any curve
connecting state 1 to state 2
• Path Function = depends on the
process; may be associated with
area under the path rather than
individual points on the path
© McGraw Hill LLC 9
 Example 2.4
When a system is taken from state
a to state b along path acb, 100 J
of heat flows into the system and
the system does 40 J of work.
A.) How much heat flows into the
system along path aeb if the work
done by the system is 20 J?

B.) The system returns from b to a

along path bda. If the work done on
the system is 30 J, does the system
absorb or liberate heat? How much?

© McGraw Hill LLC 10

 2.6: The Reversible Process
• A reversible process:
– Is frictionless
– Is never more than differentially removed from equilibrium
– Traverses a succession of equilibrium states
– Is driven by forces whose imbalance is differential (infinitesimal) in
magnitude
– Can be reversed at any point by a differential change in external
conditions
– When reversed, retraces its forward path, and restores the initial state of
the system and surroundings
• A reversible process is ideal in that it produces the best possible
result (minimum work input or maximum work output)
• To approximate a real process, values from the reversible
process are combined with an appropriate efficiency
© McGraw Hill LLC 11
 2.7: Closed-System Reversible Processes
• In general…
• The energy balance for 1 mole of a fluid in a closed system is:
dU = dQ +dW
Where Q and W represent total work, and U is the molar internal energy

• The work for a mechanically reversible, closed system is:

dW = -PdV
Where P and V are the pressure and molar volume, respectively

• Combining:
dU = dQ – PdV (2.7)

© McGraw Hill LLC 12

 Constant-Volume Process
• For constant molar volume in a closed system, the last term
of Eq. 2.7 is zero:
– Resulting in dU = dQ (2.8)
– Upon integration: ∆U = Q (2.9)

• Therefore, the heat transferred in a mechanically reversible,

constant-volume, closed-system process equals the internal
energy change of the system.

© McGraw Hill LLC 13

 Constant-Pressure Process
• Rearranging for dQ in Eqn. 2.7:
dQ = dU +PdV = d(U + PV )
• The grouping U + PV is very common and for convenience
suggests the introduction of a new thermodynamic property.
• Hence the definition of enthalpy, H :
H = U + PV (2.10)
• And thus, for a constant pressure process: dH = dQ (2.11)
• Upon integration: ∆H = Q (2.12)
• Therefore, the heat transferred in a mechanically reversible,
constant-pressure, closed-system process equals the
enthalpy change of the system.
© McGraw Hill LLC 14
 Enthalpy
H = U + PV
• Equations 2.11 and 2.12 appear in a variety of energy
balances for flow processes, including for heat exchangers,
evaporators, distillation columns, pumps, compressors,
turbines, engines, etc.
• Because U, P, and V are all state functions, H is also a state
function, and H is an intensive property of matter.

• Note that Eq. 2.10 (H = U + PV ) is the ONLY definition for

enthalpy – it is simply a conveniently defined parameter for a
common grouping of variables.

© McGraw Hill LLC 15

 2.8: Heat Capacity
• Defined as the energy required, per unit temperature, to
increase the temperature of a substance
𝜕𝑈
• At constant volume: 𝐶𝑉 ≝ (2.15)
𝜕𝑇 𝑉

– By rearrangement, for a constant V process: dU = CV dT (2.16)

𝑇
– By integration: ∆𝑈 = ‫ 𝑇׬‬2 𝐶𝑉 𝑑𝑇 (2.17)
1

𝜕𝐻
• At constant pressure: 𝐶𝑃 ≝ (2.19)
𝜕𝑇 𝑃

– By rearrangement, for a constant P process: dH = CP dT (2.20)

𝑇
– By integration: ∆𝐻 = ‫ 𝑇׬‬2 𝐶𝑃 𝑑𝑇 (2.21)
1

© McGraw Hill LLC 16

 Example 2.7
Air at 1 bar and 298.15 K is compressed to 3 bar and 298.15 K by
two different closed-system mechanically reversible processes:
a) Cooling at constant pressure followed by heating at constant volume
b) Heating at constant volume followed by cooling at constant pressure

Calculate the heat and work requirements and U and U of the air for each
path. The following heat capacities for air may be assumed independent of
temperature:
CV = 20.785 and CP = 29.100 Jmol-1K-1
Assume also that air remains a gas for which PV/T is a constant, regardless of
the changes it undergoes. At 298.15 K and 1 bar the molar volume of air is
0.02479 m3mol-1.

© McGraw Hill LLC 17

 ®
Because learning changes everything.

Section 2.9
Mass & Energy Balances for Open Systems

Copyright 2022 © McGraw Hill LLC. All rights reserved. No reproduction or distribution without the prior written consent of McGraw Hill LLC.
 Measures of Flow
• Mass flowrate: 𝑚ሶ
• Molar flowrate: 𝑛ሶ
• Volumetric flowrate: q
• Velocity (scalar): u
• Relationships: 𝑚ሶ = 𝑀𝑛ሶ and q = uA
• Mass or molar flowrate: uAρ (where ρ is specific or molar
density)

© McGraw Hill LLC 19

 Mass Balance for Open Systems
• General mass balance:
𝑑𝑚𝐶𝑉
+ ∆ 𝑚ሶ 𝑓𝑠 = 0
𝑑𝑡
: exit-entrance

∆ 𝑚ሶ 𝑓𝑠 = 𝑚ሶ 3 − 𝑚ሶ 1 − 𝑚ሶ 2

• The Continuity Equation:

𝑑𝑚𝐶𝑉
+ ∆ 𝜌𝑢𝐴 𝑓𝑠 = 0
𝑑𝑡
• At steady state: (ρuA)fs = 0
• For a single inlet, single outlet:
*control volume: the region of space
ρ1u1A1 = ρ2u2A2 identified for analysis of open systems

© McGraw Hill LLC 20

 The General Energy Balance
• Defining the accumulation of internal energy in a specific
control volume:
– Include the internal energy, potential energy, and kinetic energy of
each flowing stream
– Include heat transfer rate and the work rate

𝑑 𝑚𝑈 𝐶𝑉 1 2
= −∆ 𝑈 + 𝑢 + 𝑧𝑔 𝑚ሶ + 𝑄ሶ + 𝑤𝑜𝑟𝑘 𝑟𝑎𝑡𝑒
𝑑𝑡 2 𝑓𝑠

© McGraw Hill LLC 21

 Figure 2.5

© McGraw Hill LLC 22

 Work Rate
• Several forms of work:
– Viscous work : negligible for most applications in this course
– PV work : work of flowing streams through entrance and exits
𝑃𝑉 𝑊𝑜𝑟𝑘 = −∆ 𝑃𝑉 𝑚ሶ 𝑓𝑠

– Shaft work : work done by moving, mechanical parts on the control

volume

• Including these into the general energy balance:

𝑑 𝑚𝑈 𝐶𝑉 1 2
= −∆ 𝑈 + 𝑢 + 𝑧𝑔 𝑚ሶ + 𝑄ሶ − ∆ 𝑃𝑉 𝑚ሶ 𝑓𝑠 + 𝑊ሶ 𝑠
𝑑𝑡 2 𝑓𝑠

Where 𝑊ሶ 𝑠 indicates shaft work

© McGraw Hill LLC 23

 Simplified Energy Balance

𝑑 𝑚𝑈 𝐶𝑉 1 2
= −∆ 𝑈 + 𝑢 + 𝑧𝑔 𝑚ሶ + 𝑄ሶ − ∆ 𝑃𝑉 𝑚ሶ 𝑓𝑠 + 𝑊ሶ 𝑠
𝑑𝑡 2 𝑓𝑠
𝑑 𝑚𝑈 𝐶𝑉 1 2
= −∆ 𝐻 + 𝑢 + 𝑧𝑔 𝑚ሶ + 𝑄ሶ + 𝑊ሶ 𝑠
𝑑𝑡 2 𝑓𝑠

𝑑 𝑚𝑈 𝐶𝑉 1 2
+∆ 𝐻+ 𝑢 + 𝑧𝑔 𝑚ሶ = 𝑄ሶ + 𝑊ሶ 𝑠 (2.27)
𝑑𝑡 2 𝑓𝑠

© McGraw Hill LLC 24

 Energy Balances for Steady-State Processes
• For steady-state, single entrance, single exit processes:
1 2
∆ 𝐻+ 𝑢 + 𝑧𝑔 𝑚ሶ = 𝑄ሶ + 𝑊ሶ 𝑠 (2.30)
2
1 2 𝑄ሶ 𝑊ሶ 𝑠
∆ 𝐻 + 𝑢 + 𝑧𝑔 = + = Q + W𝑠
2 𝑚ሶ 𝑚ሶ
∆𝑢2
∆𝐻 + + 𝑔∆𝑧 = Q +W𝑠 (2.31)
2

• All terms represents energy per unit mass of fluid.

• Often, kinetic and potential energy terms are negligible:

∆𝐻 = Q +W𝑠 (2.32)

© McGraw Hill LLC 25