Chapter 2:

The First Law and Other Basic Concepts

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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
• Found that the original temperature could be restored by
transfer of heat by contact with cooler object
• Demonstrated relationship between heat & work

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 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

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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 the system
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 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 directly affect the
total internal energy of the system (∆Ut), or:
∆Ut = Q + W (2.3)
or
dU = dQ + dW
t (2.4)

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Extensive vs. Intensive Properties

• Definitions:
– Extensive properties: dependent on the quantity of a material
• Ex. total volume (Vt ), total internal energy (Ut )

– Intensive properties: not dependent on the quantity of a material

• Ex. temperature (T ), pressure (P )

Intensive properties define state of the system

• 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)
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 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). This is
known as thermal equilibrium which is the basis of Zeroeth Law of
Thermodynamics
– 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)

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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 and H)
– Path Function: property that does depend on the path taken between
two states (prototypical examples are Q andW )

• Differential state functions represent differential changes

!" %"
!
= − = ∆ and %
$ = $ − $ = ∆$
# #

• Differential path functions represent amounts, not changes

dQ = Q and dW = W
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 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

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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
• To approximate a real process, values from the reversible
process are combined with an appropriate efficiency

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 Reversible Expansion of a Gas

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Reversible Chemical Reaction

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 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)

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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)
This is also known as ISOCHORIC Process

• Therefore, the heat transferred in a mechanically reversible,

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

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 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)
This is also known as ISOBARIC Process
• 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
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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

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2.8: Heat Capacity

• Defined as the energy required, per unit temperature, to
increase the temperature of a substance
*+
• At constant volume: (% ≝ (2.15)
*, %

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

,"
– By integration: ∆. = ,# %
( / (2.17)

*0
• At constant pressure: (! ≝ (2.19)
*, !

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

,"
– By integration: ∆1 = ,# !
( / (2.21)

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 2.9: Mass & Energy Balances for Open Systems
Measures of Flow
• Mass flow rate: 23 = m/t
• Molar flow rate: 43 = n/t
• Volumetric flow rate: q
• Velocity (scalar): u = q/(t A)
• Relationships: 23 = 743 and q = uA
• Mass or molar flow rate: uAρ (where ρ is specific or molar
density)

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Mass Balance for Open Systems

• General mass balance:
29%
+ ∆ 23 ;< = 0
:

∆ 23 ;< = 23> − 23 − 23

• The Continuity Equation:

29%
+ ∆ ?@A ;< = 0
:
• At steady state: (ρuA)fs = 0
• For a single inlet, single outlet:
ρ1u1A1 = ρ2u2A2

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 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

2. 9% 1
= −∆ . + @ + EF 23 + G3 + HIJK JL:M (N3 O)
: 2 ;<

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Figure 2.5

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 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
$ (NIJK) = −∆ $ 23 ;<

– Shaft work – work of moving, mechanical parts on the control volume

• Including into the general energy balance:

2. 9% 1
= −∆ . + @ + EF 23 + G3 − ∆ $ 23 ;< + N3<
: 2 ;<

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Simplified Energy Balance

2. 9% 1
= −∆ . + @ + EF 23 + G3 − ∆ $ 23 ;< + N3<
: 2 ;<
2. 9% 1
= −∆ 1 + @ + EF 23 + G3 + N3<
: 2 ;<

P Q+ RS
+∆ 1 + @ + EF 23 = G3 + N3< (2.27)
PT ;<

Often, kinetic and potential energy terms are negligible:

P Q+ RS
+ ∆ 123 ;< = G3 + N3< (2.28)
PT

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 Energy Balances for Steady-State Processes
• For steady-state, single entrance, single exit processes:
∆ 123 = G3 + N3<

• Extensive: ∆13 T = G3 + N3<

• Intensive: ∆H = Q + Ws (2.32)

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 2.10: Synopsis
2.10 SYNOPSIS

After studying this chapter, including the end-of-chapter problems, one should be
able to:

• State and apply the first law of thermodynamics, making use of the
appropriate sign conventions

• Explain and employ the concepts of internal energy, enthalpy, state function,
equilibrium, and reversible process

• Explain the differences between state functions and path-dependent

quantities such as heat and work

• Calculate changes in state variables for a real process by substituting a

hypothetical reversible process connecting the same states

• Relate changes in the internal energy and enthalpy of a substance to changes

in temperature, with calculations based on the appropriate heat capacity

• Construct and apply mass and energy balances for open systems
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