Lecture 15

Lecture 15
Thermochemistry and
Thermodynamics
Instructor Dr. Huỳnh Kim Lâm
(huynhkimlam.iu@gmail.com)
TAs chemengtas@googlegroups.com
Lectures Wed. morning (A2.307)
Thur. afternoon (A2.407)
Office hours Wed. afternoon (Rm. A1.712)
Thur. morning (Rm. A1.712)
Communication www.blackboard.hcmiu.edu
https://www.facebook.com/groups/2017.Spring.ChemEng
Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 15 | Semester 2: 2016-2017
1 huynhkimlam.iu@gmail.com / lamhuynh.net
Definitions
A chemical or physical change is always accompanied by a

change in the energy that the matter contains
Thermochemistry is the study which deals with the heat

involved in chemical and physical changes.
Thermodynamics is the branch of physical science

concerned with heat and its transformations to and from
other forms of energy.
• Forms of energy: solar, electrical, nuclear, and chemical ≡ potential energy and kinetic
energy on the atomic and molecular scales
Thermochemistry: hóa nhiệt

2 Thermodynamics: động nhiệt học
System & Surroundings
Scientists conceptually divide the universe into
• the system: the subject/part being studied
• the surroundings: everything else relevant to the change
Universe System Surroundings
Ex: a flask containing a solution

 The system ≡ the contents of the flask
 The surroundings ≡ the flask itself, the other equipment, and perhaps the
rest of the laboratory
The
The surroundings
system
3
Energy Flow to and from a System
Universe System Surroundings
If there is energy difference, there is energy transfer (high → low)
Energy of system decreases Energy of system increases

Copyright @ 2007by The McGraw-Hill Companies, Inc.
Energy transfer outward from the system or inward from

4 the surroundings can appear in two forms, heat and work
Heat and Work – Two Forms of Energy Transfer
Heat (or thermal energy, symbol q)

 the energy transferred between a system and its
surroundings as a result of a difference in their
temperatures only (∆T ≠ 0)
Work (denoted by w)
 the energy transferred when an object is moved a
distance (d) by a force (F).
ur ur ur
w = F´ d
5
A System Losing/Gaining Energy as Heat only
Copyright @ 2007by The McGraw-Hill Companies, Inc.
The energy flow stops at thermal equilibrium:

Tsystem = Tsurroundings
6
A System Losing Energy as Work only
Zn(s) + HCl(aq) = H2(g) + ZnCl2(aq)
Copyright © 2007 by The McGraw-Hill

The energy flow stops at equilibrium: Companies, Inc
PHydrogen = Patm
7
Internal Energy
Internal Energy (U) is the total energy contained

within the system
 partly as kinetic energy and
 partly as potential energy
Kinetic involves three types of molecular motions ...
Translation Rotation Vibration
8
Vibration
1. Stretching: the rhythmic movement along a bond axis with a
subsequent increase and decrease in bond length
2. Bending: a change in bond angle or movement of a group of

atoms with respect to the rest of the molecule.
In-plane bending
Out of plane bending
Internal Energy
Potential energy involves intramolecular interactions ...
and intermolecular interactions ...
10
Energy and Temperature
Thermal Energy
 Kinetic energy associated with random molecular motion.
 Proportional to temperature (generally)
 An intensive property
Intensive property (bulk property): is a physical property of a
system that DOES NOT depend on the system size or the
amount of material in the system
(opposite to extensive property)
11
Conservation of Energy
In interactions between a system and its surroundings the

total energy remains constant
Energy is neither created nor destroyed.
∆Energysystem + ∆Energysurroundings = 0
∆Energysystem = - ∆Energysurroundings
12
System and Surroundings
The total change in the system's internal energy is the sum of

the heat (q) and work (w):
∆U = q + w
Energy is always conserved: it changes from one form into

another, moving into or out of the system, but the total
quantity of energy in the universe (system plus surroundings)
is constant.
13
Heats of Reaction, 𝒒𝒓𝒙𝒏
𝒒𝒓𝒙𝒏 = ∆𝑬𝒏𝒆𝒓𝒈𝒚 = 𝑬𝒏𝒆𝒓𝒈𝒚𝒑𝒓𝒐𝒅𝒖𝒄𝒕(𝒔) − 𝑬𝒏𝒆𝒓𝒈𝒚𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕(𝒔)
Exothermic reactions
 Produces heat, qrxn < 0
Endothermic reactions
 Consumes heat, qrxn > 0
Note: the reference point is the system, NOT the surroundings
14
Calorimetry
Calorimetry
 A technique used to measure heat exchange in chemical
reactions
 Based on the law of conservation of energy
∆Esystem = - ∆Esurroundings
A calorimeter is the device used to make heat

measurements (through ∆Esurroundings )
15
Constant-Pressure Calorimeter
∆Esystem = - ∆Esurroundings
qrxn = -qcal
16
Constant-volume Calorimeter
Bomb Calorimeter
qrxn = -qcal
qcal = qbomb + qwater + qwires +…
Define the heat capacity of the calorimeter:
𝑞𝑐𝑎𝑙 = ෍ 𝑚𝑖𝑐𝑖 ∆𝑇 = 𝐶𝑐𝑎𝑙 ∆𝑇

𝑎𝑙𝑙 𝑖
𝐶𝑐𝑎𝑙 is known for a specific calorimeter since

all components are known.
17
Work (w)
Work (w) is the energy transferred when an

object is moved by a force.
𝒘=𝑭×𝒅
where
• w is work,
• F is the force, and
• d is the distance over which the force is exerted.
18
Work (w)
Pressure–Volume (PV) work is the work of compression

(or expansion) of a gas
Ideal gas law: PV = nRT

19
Work (w)
In addition to heat effects chemical reactions may also do work
Gas formed pushes against the

atmosphere.
• Volume changes.
• Pressure is constant
 Pressure-volume (PV) work.
20
Calculating work (w)
PV work is calculated as follows:
w = –P DV= –P (Vfinal – Vinitial)
Focus on the system (reference point): gain (+) or lose (-)

energy?
Energy entering a system carries a positive sign: if heat is absorbed

by the system, q > 0. If work is done on a system, w > 0
Energy leaving a system carries a negative sign: if heat is given off

by the system, q < 0. If work is done by a system, w < 0
21
State of a System
The state of a system refers to its exact condition,

determined by
 the kinds of matter present
 the amounts of matter present,
 the structure of this matter at the molecular level
 the prevailing pressure and temperature
Example: internal energy (U) is a function of the state of the

system ...
22
State Functions
A state function is a property

that has a unique value that
depends only on the present
state of a system and NOT on
how the state was reached,
nor on the history of the
system
DU = Ufinal – Uinitial
Energy is a state function; therefore, the same ∆U can occur

through any combination of q and w.
23
State Functions - Example
24
First Law of Thermodynamics
The Law of Conservation of Energy

“In a physical or chemical change, energy can be exchanged
between a system and its surroundings, but no energy can be
created or destroyed”
The change in U is related to the energy exchanges that occur as

heat (q) and work (w)
DU = q + w
Energy is neither created nor destroyed.

In other words, the total energy of the universe is a constant; if the
system loses energy, it must be gained by the surroundings, and
vice versa.
25
Internal Energy Change at Constant Volume
DU = q + w
For a system where the reaction is

carried out at constant volume:
DV = 0 (thus w = P∆V=0)
→DU = qV.
All the thermal energy produced

by conversion from chemical
energy is released as heat; no P-V
work is done.
At constant volume
∆U = qv
26
Internal Energy Change at Constant Pressure
DU = q + w
For a system where the reaction is

carried out at constant pressure
DU = qP – PDV
OR
qP = DU + PDV
 Most of the thermal energy is

released as heat.
 Some work is done to expand the

system against the surroundings
(push back the atmosphere) At constant pressure
qP = ∆U + P∆V
27
Enthalpy and Enthalpy Change
The evolved H2 pushes

Enthalpy is the sum of the back the atmosphere;
internal energy and the work is done at
constant pressure.
pressure-volume product of
a system:
H = U + PV
Zn + 2 HCl  ZnCl2 + H2
For a process carried out
at constant pressure,
qP = DU + PDV
 qP = DH
Unknown source Most reactions occur at constant
pressure, so for most reactions, the heat
evolved equals the enthalpy change.
28
Properties of Enthalpy
Two logs on a fire give
off twice as much heat
as does one log.
Enthalpy is an extensive property.

 It depends on how much of the substance is present.
Since U, P, and V are all state functions, enthalpy H must

be a state function also.
Enthalpy changes have unique values.

DH = qP
29
Using ∆H
 Values are measured experimentally
 Negative values indicate exothermic reactions

 𝑞𝑃 = ∆𝐻 < 0
 Positive values indicate endothermic reactions

 𝑞𝑃 = ∆𝐻 > 0
 Changes sign when a process is reversed. Therefore, a

cyclic process has the value ∆𝐻 = 0
 For problem-solving, one can view heat being absorbed in

an endothermic reaction as being like a reactant and heat
being evolved in an exothermic reaction as being like a
product
 Exothermic: Reactants = Products + Q
30  Endothermic: Reactants + Q = Products
Hess’s Law
A + 2B = C (Eq. 1)
C = 2D (Eq. 2)
A + 2B =2D (Eq. 3)
(Eq. 3) = (Eq. 2) + (Eq. 1)
 ∆H3 = ∆H1 + ∆H2
31
Hess’s Law - Example
Eq. 1: S(s) + O2(g) → SO2(g) ∆H1 = - 296.8 kJ
Eq. 2: 2SO2(g) + O2(g) → 2SO3(g) ∆H2 = - 198.4 kJ
Eq. 3: S(s) + 3/2O2(g) → SO3(g) ∆H3 = ?
(Equation 3) = (Equation 1) + ½(Equation 2)
 ∆H3 = ∆H1 + ½ (∆H2) =-396 kJ
32
Enthalpies of Formation, DHf
DHf is the enthalpy change when one mole of the compound is made
from the elements in their stable states at that pressure and
temperature
Ex: enthalpy of formation of CH4 at 1 atm and 298 K?

C(s) + 2H2(g) = CH4(g)
⇒ ∆𝐻𝑓 CH4 , 298 𝐾 = ∆𝐻𝑟𝑥𝑛 (C(s) + 2H2(g) = CH4(g))

= 𝐻 CH4 − 𝐻 C s − 2𝐻 H2
Unit: cal/mol OR J/mol
33
Standard State Conditions
The standard state of a solid or liquid substance is the pure element or
compound at 1 atm pressure and the temperature of interest (usually
298.15 K or 25oC)
The standard state of a gaseous substance is the “ideal gas” at 1 atm

pressure and the temperature of interest
Ex: at 1 atm, 25oC standard state for Hg is liquid, C is solid, water is

liquid, He is gas
0
The standard enthalpy of reaction (∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ) is the enthalpy change for a
reaction in which the reactants in their standard states yield products in
their standard states
The standard (molar) enthalpy of formation (∆𝐻𝑓0 ) of a substance is

equal to the enthalpy change when one mole of the compound is formed
at its standard state (at a constant pressure of 1 atm and a fixed
temperature, ordinarily 25oC) from the elements in their stable states at that
pressure and temperature.
34
Standard Enthalpy/Heat of Formation, DHfo
superscript o means standard
ΔHf
state 25oC and 1 atm pressure
o
subscript f means formation
from most stable elements
DHfo(CO2) = ?
DHfo(CO2) is defined as the enthalpy change for
C(s, graphite) + O2(g) → CO2(g)
at standard state 25oC and 1 atm pressure
DHfo of an element is taken to be zero
Ex: DHfo (O2(g)) = DHfo (Br2(l)) = 0
DHfo of ions in aqueous solution are relative values, established by

taking DHfo (H+(aq)) =0
35
Reaction Enthalpy
DH rxn
o
 H product(s)
o
 H reactant(s)
o
Can be calculated from DHof
DHorxn = S(np × DHof (products)) – S(nr × DHof (reactants))
where np and nr are stoichiometric coefficients.
 For organic compounds, the measured DHorxn is often the standard

enthalpy of combustion DHocomb
36
Enthalpies from Bond Energies
The bond enthalpy (D) is defined as when one mole of

bonds is broken in the gaseous state
Calculate the enthalpy of formation of water vapor from

bond energies (D)
H2(g) + 1/2O2(g)  H2O(g)
Given: D(H-H) = 432 (kJ/mol)
D(O-O) = 494 (kJ/mol)
D(H-O) = 459 (kJ/mol)
(The experimental value is 241.8 kJ/mol)
37
Enthalpy of Solution (DHsoln)
The enthalpy of solution (DHsoln) is the heat generated or
absorbed when a certain amount of solute dissolves in a certain
amount of solvent.
Heats of Solution of Some Ionic

Compounds
DHsolution = Hsolution - Hcomponents
38
Entropy and the 2nd Law of Thermodynamics
Two trends in nature
1. ∆E ≠ 0: high energy  low energy
2. ∆E = 0: order  disorder
Note that: combination of both in real processes

39
Entropy
What is the criterion that holds true for

all spontaneous processes?
Answer: All spontaneous processes must

have an increase in entropy
What is entropy (S)?
A spontaneous process is a self-sustaining action

40 (quá trinh tự xảy ra)
Entropy
Copyright 2006 Pearson Prentice Hall, Inc.
• Irreversible processes cannot be undone by exactly

reversing the change to the system.
Ex: C3H8 + 5O2  3CO2 + 4H2O
• Spontaneous processes are irreversible
41
Entropy
• Thought of as a measure of the randomness of a system.

• Molecular view: it is related to the various modes of
motion in molecules.
• Entropy is a state function
(Like total energy, E, and enthalpy, H)
=> Therefore,
DS = Sfinal  Sinitial
42
Entropy - Calculation
For a process occurring at constant temperature

(an isothermal process):
𝑞𝑟𝑒𝑣
∆𝑆 =
𝑇
 qrev: the heat that is transferred when the process is

carried out reversibly at a constant temperature.
 T: temperature in Kelvin.
43
Second Law of Thermodynamics
All real processes occur spontaneously in the direction that

increases the entropy of the universe (system + surroundings)
The entropy of the universe does not change for reversible processes
and increases for spontaneous processes.
Reversible process (ideal):

∆𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = 0
Irreversible process (real, spontaneous):

∆𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 > 0
44
Standard Entropies, So
These are molar entropy values of

substances in their standard states.
Standard entropies tend to increase

with increasing molar mass.
45
Entropy on the Molecular Scale
With more microstates in which the energy can be dispersed,

the entropy tends to increase with increases in
 Temperature
 Volume (gases)
 The number of independently moving molecules
46
Entropy change
So increases as the temperature rises
T (K) 273 295 298

So for Cu
31.0 32.9 33.2
[J/mol-K]
47
Entropy change
So increases for a substance as it changes from
a solid to a liquid to a gas
The increase in entropy from

liquid to gas is much larger
than that from solid to liquid:
∆Sovaporation >> ∆Sofussion
48
Entropy change
Dissolving a solid or liquid

The entropy of a dissolved solid or liquid is
usually greater than the entropy of the
pure solute, but the nature of solute and
solvent and the dissolving process
affect the overall entropy change
The entropy change

accompanying
the dissolution of a salt
49
Entropy change
Dissolving a gas in a liquid/solid:

The entropy is always less than the
entropy of the gas
Dissolving in another gas:

the entropy increases from the mixing of
the molecules
50
Entropy change
So increases with the increase in the number of gas

molecules or the number of moles.
51
Entropy change
Differences in entropy values for substances in the same

phase are based on atomic size and molecular complexity.
For elements (and similar compounds) within a periodic group, energy

levels (microstates) become closer together for heavier atoms, so entropy
increases down the group
For compounds, entropy increases with chemical complexity, that is, with
the number of atoms in a formula unit or molecule of the compound
52
The third law of Thermodynamics
A perfect crystal has zero entropy at a temperature of

absolute zero:
Ssys = 0 at 0 K.
(absolute entropy of a substance)
"Perfect" means that all the particles are aligned flawlessly in the
crystal structure, with no defects of any kind
53
Standard Entropy of Reaction, ∆𝑆𝑟𝑥𝑛
Entropy changes for a reaction can be calculated the same
way we used for DH:
∆𝑺𝒓𝒙𝒏 = ෍ np × 𝑺𝒐𝒊 (𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − ෍ nr × 𝑺𝒐𝒊 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)
 np and nr are stoichiometric coefficients

 S° for each component is found in a table.
 Note for pure elements:
𝑆𝑜 ≠ 0
∆𝐻 𝑜 = 0
if the number of moles of gas increases, ∆𝑆𝑟𝑥𝑛 is usually

positive; if the number decreases, ∆𝑆𝑟𝑥𝑛 is usually negative.
54
Standard Entropy of Reaction, ∆𝑆𝑟𝑥𝑛 =Sproduct(s)-Sreactant(s)
Exothermic change
qsys < 0; qsurr > 0 and ∆Srxn > 0
Endothermic change
qsys > 0; qsurr < 0 and ∆Srxn > 0
55
Free Energy, G
G = H - TS
Free-energy Change
∆G = ∆H - T∆S
Standard Free-energy Change
∆Go = ∆Ho - T∆So

When all components of the system are in their
standard states
56
Standard Free Energy changes
Standard free energies of formation, DGf are analogous to

standard enthalpies of formation, DHf.
𝑜
∆𝐺𝑜𝑟𝑥𝑛 = ෍ 𝑚 × ∆𝐺𝑓,𝑖 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑛 × ∆𝐺𝑓𝑜 𝑖 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
∆𝐺𝑓𝑜 can be looked up in tables,

OR
calculated from S° and DH
57
Standard Free Energy Changes
∆Grxn < 0: spontaneous at all T

∆Grxn > 0: nonspontaneous at all T
58
59
∆𝑮𝒐𝒓𝒙𝒏 = −𝑹𝑻𝒍𝒏𝑲𝒆𝒒
60
Essential Terms/Concepts/Equations
Thermochemistry Nhiệt hóa học
Thermodynamics Nhiệt động học
Internal energy Nội năng
Kinetic energy Động năng
Potential energy Thế năng
Instramolecular Nội phân tử
Intermolecular Liên phân tử
Intensive property Tính chất …
Extensive property Tính chất …
Calorimetry
Calorimeter
State function Hàm trạng thái
Enthalpy ~ “Nhiệt”
Heat of formation = enthalpy of formation Nhiệt tạo thành
Spontaneous tự xảy ra được (đồng thời)
Nonspontaneous Không xảy ra được (Không đồng thời)
Reversible / Irreversible Thuận nghịch / không thuận nghịch
Isothermal process Quá trình đẳng nhiệt
61
Problem 1
What is the standard free-energy change, DGo, for the

following reaction at 25oC?
N2(g) + 3H2(g)  2NH3(g)
H2(g) N2 (g) NH3(g)

So (J/(mol-K)) 130.6 191.6 192.7
DHof (kJ/mol) 0 0 -45.90
DHo(rxn) = 2*(-45.90) – 1*0 – 3*0 = - 91.80 kJ

So(rxn ) = 2*192.7 – 1*191.6 – 3* 130.6 = -198.0 J
DGo(rxn) = -91.80*103 – (273+25)*(-198.0) = -32796 J < 0
62
Problem 2
NaCl(s)  Na+(aq) + Cl-(aq)

(a) Calculate ∆Go at 298 K for the above reaction. ∆ Gfo can be found in Table 1
(attached).
(b) Using the ∆ Go from part (a) calculate the equilibrium constant K for this
reaction. This is the Ksp for NaCl.
(c) Using the ∆ Go from part (a) calculate the ∆ G for the reaction above at 298 K
when the concentration of Na+(aq) is 0.50 M and the concentration of Cl-(aq) is 0.75
M.
(d) If the reaction above is spontaneous at all temperatures what does this tell us
about the sign of ∆G, ∆H, and ∆S, i.e. are they positive or negative?
NaCl(s) Na+(aq) Cl-(aq)
Sof (J/(mol-K)) 72.12 59.1 56.5

Hof (kJ/mol) -411.1 -240.1 -167.2
63
End of lecture 15
Thank you!
The sign conventions
Enthalpy
Enthalpy is a state function -- it doesn’t matter

how you go from one place to another
The DH value is the same no matter how you

get from AB
DH = DU + PDV
DH = Hfinal  Hinitial
= Hproducts  Hreactants
Standard Entropy of Reaction, ∆𝑆𝑟𝑥𝑛
Exothermic change
qsys < 0; qsurr > 0 and ∆S > 0
Endothermic change
qsys > 0; qsurr < 0 and ∆S > 0
The change in entropy of the surroundings is directly related to
an opposite change in the heat of the system and inversely
related to the temperature at which the heat is transferred.
𝑞𝑠𝑦𝑠 ∆𝐻𝑠𝑦𝑠
∆𝑆𝑠𝑢𝑟𝑟 = − =−
𝑇 𝑇
Practical uses
= – Gibbs Free Energy

Make this equation nicer:
Gibbs Free Energy
TDSuniverse is defined as the Gibbs free energy, DG.
For spontaneous processes: DSuniverse > 0

And therefore: DG < 0
DG is easier to determine than DSuniverse.

So:
Use DG to decide if a process is spontaneous.
Chemistry
Chemi for Engineers
CH011IU
HK 1, 2014-2015
Huỳnh Kim Lâm
70

Lecture 15 - Thermochemistry and Thermodynamics

Încărcat de

Informații document

Titlu original

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Lecture 15 - Thermochemistry and Thermodynamics

Încărcat de

Drepturi de autor:

Formate disponibile

A chemical or physical change is always accompanied by a

Thermochemistry is the study which deals with the heat

Thermodynamics is the branch of physical science

Thermochemistry: hóa nhiệt

Universe System Surroundings

Ex: a flask containing a solution

Universe System Surroundings

If there is energy difference, there is energy transfer (high → low)

Energy of system decreases Energy of system increases

Energy transfer outward from the system or inward from

Heat (or thermal energy, symbol q)

Copyright @ 2007by The McGraw-Hill Companies, Inc.

The energy flow stops at thermal equilibrium:

Copyright © 2007 by The McGraw-Hill

Internal Energy (U) is the total energy contained

Kinetic involves three types of molecular motions ...

Translation Rotation Vibration

2. Bending: a change in bond angle or movement of a group of

Potential energy involves intramolecular interactions ...

and intermolecular interactions ...

In interactions between a system and its surroundings the

Energy is neither created nor destroyed.

The total change in the system's internal energy is the sum of

Energy is always conserved: it changes from one form into

𝒒𝒓𝒙𝒏 = ∆𝑬𝒏𝒆𝒓𝒈𝒚 = 𝑬𝒏𝒆𝒓𝒈𝒚𝒑𝒓𝒐𝒅𝒖𝒄𝒕(𝒔) − 𝑬𝒏𝒆𝒓𝒈𝒚𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕(𝒔)

Note: the reference point is the system, NOT the surroundings

A calorimeter is the device used to make heat

qcal = qbomb + qwater + qwires +…

Define the heat capacity of the calorimeter:

𝑞𝑐𝑎𝑙 = ෍ 𝑚𝑖𝑐𝑖 ∆𝑇 = 𝐶𝑐𝑎𝑙 ∆𝑇

𝐶𝑐𝑎𝑙 is known for a specific calorimeter since

Work (w) is the energy transferred when an

Pressure–Volume (PV) work is the work of compression

Ideal gas law: PV = nRT

In addition to heat effects chemical reactions may also do work

Gas formed pushes against the

 Pressure-volume (PV) work.

Focus on the system (reference point): gain (+) or lose (-)

Energy entering a system carries a positive sign: if heat is absorbed

Energy leaving a system carries a negative sign: if heat is given off

The state of a system refers to its exact condition,

Example: internal energy (U) is a function of the state of the

A state function is a property

Energy is a state function; therefore, the same ∆U can occur

The Law of Conservation of Energy

The change in U is related to the energy exchanges that occur as

Energy is neither created nor destroyed.

For a system where the reaction is

All the thermal energy produced

For a system where the reaction is

 Most of the thermal energy is

 Some work is done to expand the

The evolved H2 pushes

Enthalpy is an extensive property.

Since U, P, and V are all state functions, enthalpy H must

Enthalpy changes have unique values.

 Negative values indicate exothermic reactions

 Positive values indicate endothermic reactions

 Changes sign when a process is reversed. Therefore, a

 For problem-solving, one can view heat being absorbed in

(Eq. 3) = (Eq. 2) + (Eq. 1)

 ∆H3 = ∆H1 + ∆H2

DHo(rxn) = 2(-45.90) – 10 – 3*0 = - 91.80 kJ