Thermodynamics: The First Law

Atkins, Chapter 2

Open System: Mass, heat, energy flow freely

Closed System: Heat, energy flow freely
Isolated System: No mass, heat, or energy flow
System

System System

HEAT HEAT

q<0 q>0
Nils Walter: Chem 260
Exothermic Endothermic
 Internal Energy U
Internal Energy U:
The sum of all of the kinetic and potential energy contributions to the energy
of all the atoms, ions, molecules, etc. in the system

He gas Methanol Gas

Translational Energy Rotational Energy

Electronic Energy Vibrational Energy

Nuclear Energy Bond Energy

Nils Walter: Chem 260
 The First Law of Thermodynamics:
Internal Energy is Conserved
The
Thechange
changein ininternal
internalenergy
energy(U)
(U)of
ofaaclosed
closedsystem
systemisis
equal
equalto
tothe
thesum
sumofofthe
theheat
heat(q)
(q)added
addedtotoititand
andthe
thework
work(w)(w)
done
doneupon
uponitit
The
Theinternal
internalenergy
energyofofan
anisolated
isolatedsystem
systemisisconstant
constant

U = q + w For a Closed System

U = 0 For an Isolated System

Internal energy U is a state function

Quantity is independent of path
Volume, Temperature, Pressure,
and Quantity are other examples
of state functions
Nils Walter: Chem 260
 Internal Energy can be exchanged with
the surroundings as heat or work
Closed system,
U = q + w expansion against
external pressure
Closed system,
constant volume

Heat is stored as internal

energy and released as
q heat introduced
volume-pressure work [J]

T
U = q + w
w = -Fdx = -pV = q - pexV
w = 0; no work done

U = q v
Nils Walter: Chem 260
 Internal Energy and Enthalpy
Enthalpy definition: = U + pV
Most convenient for processes at constant pressure:
Cooking dinner Digesting dinner
Drying the laundry Synthesizing a compound in lab

At constant pressure, if only pV work is done:

V2
U = q + w = qp - p dV
V1
V2
= qp - p dV = qp - p(V2-V1) = qp - p
V
V1
p independent of V
Enthalpy is the heat transferred
= U V = q p
+ p in a process at constant pressure
(assuming only pV work)
Nils Walter: Chem 260
 Enthalpy
Open System: Mass, heat, energy flow freely
Closed System: Heat, energy flow freely
Isolated System: No mass, heat, or energy flow
System

System System

HEAT HEAT

q<0 q>0
Nils H > 0Chem 260
Exothermic H < 0
Walter:
Endothermic
Enthalpy and Internal Energy are
State Functions
We only need be concerned with the change in enthalpy ( H) or
U), not the path of how we got there
change in internal energy (

We can arbitrarily assign H = 0 for each element in its

standard state = state of aggregation at p = 1 bar, T = 298.15 K

Standard Formation Reaction: Formation of

fH = standard molar enthalpies

one mole of a substance from the elements in

their standard states.
CS2 (l) +87.86 kJ/mol C(graphite) + 2 S(s, rhombic) CS2(l)
of formation

C(graphite) C(graphite)
0
O2 (g), S(s, rhombic)

CO (g) -110.52 kJ/mol C(graphite) + 1/2 O2 (g) CO(g)

C(graphite) +O2 (g) CO2(g)
CO2 (g) -393.51 kJ/mol Nils Walter: Chem 260