Chapter 2: Fundamentals of Materials Synthesis

92.1 Materials Science Tetrahedron

92.2 Structure of materials?
92.3 Thermodynamics of solids
92.5 Phase diagrams
92.6 Chemical thermodynamics
92.7 Chemical kinetics
92.8 Generalized transport law

Materials Science Tetrahedron

Performance
/Application

Characterization

Processing
Properties
/Synthesis

Microtructure
/Composition
 Property of Materials, Processing, & Performance

™ Processing: how to manufacture or synthesize the

materials
™ Property: response to a specific imposed stimulus:
− Mechanical property: load
− Electrical property: electric field
− Thermal property: heat
− Optical property: electromagnetic or light radiation
™ Performance: the functionality of the material in a
given environment (usually cost is also a factor:
performance-to-cost ratio)

Application of the Tetrahedron of Materials Science &

Engineering to LIB Electrode Materials
Safety, practical capacity,
rate capability, cost
compared to other
materials and production
route

Ionic/electronic
conductivity, capacity,
Synthesis routes, chemical stability,
surface modification, taping density,
ball-milling, processing electrochemical
modeling, scalable stability window
production
Crystal structure,
(non)stoichiometry,
particle morphology,
particle size
distribution, surface
coating
Application of the Tetrahedron of Materials Science &
Engineering to Sheet Steels for Automotive Chassis

© 2003 Brooks/Cole Publishing / Thomson Learning™

Note that the microstruture-synthesis and processing-composition
are all interconnected and affect the performance-to-cost ratio.

Structure of Materials

¾Subatomic level: electrons within the

individual atoms and its interaction with their
nuclei

¾Atomic level: the organization of atoms or

molecules relative to one another

¾Microscopic level: microstructure subject to

direct observation using microscopes

¾Macroscopic level: macrostructure that can be

viewed with naked eye
 Scale of Structural Organization
Size Structure Method of Observation
Sub-atomic
12 orders of magnitude!
Particles Particle
<0.1 nm Accelerator
1 nm Atoms
Scanning Tunneling
Defect Structures Microscope (STM, AFM)
10 nm
in Crystals
Transmission Electron
100 nm Microscope (TEM)
1 μm
Crystallites Scanning Electron
10 μm ("Grains") Microscope (SEM)
and
100 μm Precipitates X-Ray Diffractometer
1 mm
10 mm Optical Microscope

100 mm Components
Naked Eye
1m
10 m Assemblies

The Scale of Things – Nanometers and More

Things Natural Things Manmade
10-2 m 1 cm
10 mm
Head of a pin
1-2 mm The Challenge

Ant 1,000,000 nanometers =

~ 5 mm 10-3 m 1 millimeter (mm)
Microwave

MicroElectroMechanical
Dust mite (MEMS) devices
10 -100 μm wide
200 μm 0.1 mm
10-4 m
100 μm
Microworld

Fly ash
Human hair ~ 10-20 μm
~ 60-120 μm wide
O
P
O O

10-5 m 0.01 mm O O O O

10 μm O O O O O O O O

Pollen grain
Red blood cells
Infrared

O O O O O O O O

Red blood cells

S S S S S S S S

with white cell

~ 2-5 μm 1,000 nanometers = Zone plate x-ray “lens”
10-6 m 1 micrometer (μm) Outer ring spacing ~35 nm
Visible

Fabricate and combine

nanoscale building
blocks to make useful
0.1 μm
10-7 m devices, e.g., a
100 nm photosynthetic reaction
Ultraviolet

center with integral

semiconductor storage.
Nanoworld

Self-assembled,
0.01 μm Nature-inspired structure
10-8 m Many 10s of nm
~10 nm diameter 10 nm
Nanotube electrode
ATP synthase

10-9 m 1 nanometer (nm) Carbon

buckyball
Soft x-ray

~1 nm
diameter
Carbon nanotube
~1.3 nm diameter
DNA 10-10 m 0.1 nm Quantum corral of 48 iron atoms on copper surface
~2-1/2 nm diameter Atoms of silicon positioned one at a time with an STM tip Office of Basic Energy Sciences
spacing ~tenths of nm Corral diameter 14 nm
Office of Science, U.S. DOE
Version 10-07-03, pmd
 Structure of Materials

Atomic Structure Crystal Structure

波来铁
珠光体

Microstructure Macrostructure

Atoms
Protons
Electrons electrical charge= +e

electrical charge= -e

Neutrons
Bohr Model
 Atom cubic models (1902)
Lewis, G. N. The Atom and the Molecule. J. Am. Chem. Soc. 1916, 38, 762-785

Ionic bond Intermediate state Covalent bond Double bond

Single bond: share a corner

Double bond: share an edge
Triple bond: share a face

Crystal structure:
from the viewpoint of atomic packing

ABCA

ABA
Packing mode 1
(ABCABC…)

ATOMIC PACKING FACTOR

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68
Close-packed directions:
length = 4R
= 3a
Unit cell c ontains:
1 + 8 x 1/8
= 2 atoms/unit cell
R
a
atoms volume
4
unit cell 2 π ( 3a/4 ) 3
3 atom
APF =
volume
a3
unit cell

ATOMIC PACKING FACTOR: FCC

• APF for a face-centered cubic structure = 0.74
Close-packed directions:
length = 4R
= 2a
Unit cell c ontains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
atoms volume
4
unit cell 4 π ( 2a/4 ) 3
3 atom
APF =
volume
a3
unit cell
 HEXAGONAL CLOSE-PACKED STRUCTURE
(HCP)

• ABAB... Stacking Sequence

• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

• Coordination # = 12
• APF = 0.74

7 crystal systems

http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/Strucsol.html
 14 Bravais Lattices

Coordination number and crystal geometry

r/R CN Name Geometry

0 - 0.155 2 2 Linear

0.155 - 0.225 3 Triangular

0.225 - 0.414 4 Tetrahedral

0.414 - 0.732 6 Octahedral

0.732 - 1.0 8 Cubic

1.0 12 12-fold
(not unique
 Clusters of atoms and molecules

• multiples of a simple subunit, e.g. Cn, Arn, or (H2O)n

• The cluster size n can vary and determines the properties

Small clusters have (nearly) all atoms on the surface.

Giant metal cluster growth sequence

• Core: 13-atom icosahedron (5-fold symmetry)

• Shell: 10n2+2 atoms (12, 42, 92, 162, 252)
• Total number of atoms: 13, 55, 147, 309, 561 (“Magic numbers”)
• Ex. Au55(PPh3)12Cl6 (diameter = 1.4nm);
Ni147(PPr3)12Cl24;
Au561(phen)60(OAc)180
 An example of giant metal cluster

Chem. Commun., 2003, 1282 - 1283

Au55(porphyrin)6

An example of metal cluster: application

Haruta et al. J. Catal. 115 (1989) 301

• Gold nano-particles @ α-Fe2O3, Co3O4, and NiO

prepared by co-precipitation
• Catalytic oxidation of H2 and CO with air as oxidant
 An example of metal cluster: application

Cho: Science 299 (2003) 1684

Crystal structure:
from the viewpoint of chemical bonding
™ Primary bonding (strong bonding): Bonding
is achieved when the atoms fill their outer s
and p shells
− Ionic Bonding
− Covalent Bonding
− Metallic Bonding

™ Secondary bonding (weak bonding) — van

der Waals bonding

™ Hydrogen bonding
 The Born-Lande Equation

ANZ+ Z- e2 1
Uo = 1 -
4πεoro n

™ Thus all we need to calculate

lattice energies is:
- Knowledge of the crystal structure.
- The interatomic distance, ro
™ The Born exponent depends
upon the type of ion involved.

Ion Configuration n
He 5
Ne 7
Ar, Cu+ 9
Kr, Ag+ 10
Xe, Au+ 12

Typical Values for the Madelung Constant

Compound Crystal Lattice A

NaCl FCC 1.74756
CsCl CsCl 1.76267
CaF2 Cubic 2.51939
CdCl2 Hexagonal 2.244
MgF2 Tetragonal 2.381
ZnS (wurtzite) Hexagonal 1.64132
TiO2 (rutile) Tetragonal 2.408
Hexagonal 2.2197
Al2O3 Rhombohedral 4.1719
 The Kapustinskii’s Equation.

Kapustinskii noted an empirical increase in the value of

the Madelung constant, A, as the coordination number of
the ions increased.
For a particular anion-cation pair, ro, also increases with
coordination number.

1200.5 ν Z+ Z- 0.345
U= 1 - kJ.mol-1
rc + ra rc + ra

ν: the number of ions in one formula unit.

rc + ra: in pm.

3D representation of crystal structures

 NaFeO2 and LiCoO2

Defect structures

™ 缺陷的分类(根据缺陷的尺寸)
™ (1)点缺陷，零维缺陷
™ (2) 线缺陷，一维缺陷
™ (3) 面缺陷，二维缺陷
™ (4) 体缺陷，三维缺陷
™ (5) 电子缺陷
 Point defects

错位缺陷

本征点缺陷 空位缺陷

零维缺陷 间隙缺陷
(Atomic size defects)
杂质点缺陷

取代缺陷

Silicon conductivity and defects

Defects in yttria stabilized zirconia (YSZ)

氧离子传导依赖于缺陷（氧空位）的存在和运动！

Defects in LiMO2
Lithium ion batteries

Reactivity vs. Defects

Can we manufacture materials in a very small (micron)
dimension??
Micro-Electro-Mechanical
Systems (MEMS)

2 μm

Can we manipulate atoms to prepare materials?

Yes. We can do it by means of Scanning Probe Microscopy

(SPM) that allow us to achieve atmic resolution.

Scanning Tunneling Mic. (STM)

Very Sharp Tip scans over
sample surface Atomic Force Mic. (AFM)
Magnetic Force Mic. (MFM)
Near Field Scanning Optical Mic. (NSOM)

ATOMIC RESOLUTION

• Gerd Binnig (right) and Heinrich Rohrer (IBM)

• Invented and designed the first STM in 1981
• Nobel Prize in Physics in 1986
STM

C60 observed by
STM at USTC
 Atomic Manipulation

Scanning
Probe Tip

W-tip

Atom

Atomic Manipulation

Iron atoms on a copper surface

Don Eigler, IBM

 Handmaking molecules

Wilson Ho
UC, Irvine.

Fe + 2CO = Fe(CO) 2

Handmaking molecules

C 60 + n K = K n C 60
慢工出细活定律: resolution ~ 23At0.2

“… atom manipulation
for technological
purpose is … , in
the foreseeable
D.M. Tennant
in Nanotechnology future, completely
(Springer, 1999)
ridiculous. ( I will
of course be
delighted to find
myself wrong) “ --
Don Eigler, 1999.

Laws of Thermodynamics

ΔU = q + w or dU = δq –pdV = TdS - pdV

ΔStotal ≥ 0
 An example of energy conversion
涡流式加热器

ВТГ -涡流加热器; БГВ -热水蓄水器;

ТО – 热交换器; СН1, СН2 - 泵; В1...В9 – 阀
门;
РБ - 膨胀箱; Р1...Рn - 散热器;
К1...К3 – 水龙头; ХВ - 冷水; ГВ - 热水

Power plant arrangement

Heat flows from Th to Tc, turning turbine along the way

 Power plant arrangement

Power plants these days (almost all of which are heat-engines)

typically get no better than 33% overall efficiency

What to do with the waste heat (ΔQc)?

™ One option: use it for space-heating locally

 Overall efficiency greatly enhanced by
cogeneration

Heat Pumps

Heat Pumps provide a means to very efficiently move heat

around, and work both in the winter and the summer
 Heat Pump Diagram

Laws of Thermodynamics

•Enthalpy: H ≡ U + PV
•Helmholtz Free Energy: F ≡ U - TS
•Gibbs Free Energy: G ≡ U + PV - TS ≡ H - TS

•Coefficient of thermal expansion:

Usually α > 0 (but with exception: water).

•Coefficient of compressibility β:
• Heat capacity Cp and Cv:
(Cp > Cv because Cp-Cv = Tα2V/β)

δQ rev,P = CpdTp
 Thermodynamic laws and
Maxwell relations
• For simple-closed systems:
dU = TdS – PdV
dH = TdS + VdP
dF = -SdT – PdV
dG = -SdT + VdP

• Maxwell relations:

( ∂T
∂V
)
S
= - ( ∂P )
∂S V
( ∂T∂P
)
S
= ( ∂V
∂S
)
P

( ∂∂S
∂V
)
T
= ( ∂P
∂T
∂
)
V
( ∂∂S
∂∂P
)
T
=
∂∂V
-( )
∂
∂T P

Thermodynamic state
functions in terms of T and P
 A general procedure to determine the
relationship between thermodynamic variables
1. Identify the state function Z that needs to be calculated
2. Determine the state functions X and Y that act as variables
3. Write the differential dZ in symbolic form; express the
differentials dX and dY in terms of dT and dP
4. Compare the symbolic expression for dZ in terms of dT and
dP to the given version containing experimental variables: solve
for M and N
5. Write down the desired expression for dZ in terms of dX and
dY
6. If appropriate, use the coefficient relations to relate partial
derivatives of Z to the expressions for M and N
7. If appropriate, integrate dZ from initial to final state

Gibbs’ Phase Rule

f=c–p+2
Unary: f = 3 – p Æ p = 1,2,3 Æ2-D phase diagram
Binary: f = 4 – p Æ p = 1,2,3,4 Æ3-D phase diagram
Ternary: f = 5 – p Æ p = 1,2,3,4,5 Æ3-D phase diagram
(isothermal isobaric sections)
 Lever rule

liquid phase composition

ε-phase composition
average composition

Achieving a microstructure via slow cooling

• Cool down: upon entering the α–L coexistence

region some -solid appears in the liquid. Its
amount follows from the lever rule.

• Upon further cooling, more -solid appears,

and the composition of both phases changes.

• At a certain temperature, 3-phase coexistence

arises, immediately followed by 2-phase
coexistence.

• The growth of α+β phases happens at the

expense of the liquid phase through nucleation.
Slow solidification

• The composition X2e is the eutectic composition.

 Achieving a microstructure via quenching

• Phase transformation only occurs at T tdispersion of β-phase particles

p
in an α-phase matrix.
•Immediately after the quench, the system entirely consists of the phase
at composition X20 t this is a supersaturated structure
•The growth of the β particles can be understood through the assumption
of local equilibrium at the α – β interface, which implies that at the surface
the compositions follow from the phase diagram:

Phase Equilibrium

Phase Diagrams
™ Isomorphous system
- Complete solid solubility
- 2-phase region
♦ Constant Temperature Tie-line
between equilibrium phases
- Lever rule can be used give mass
fractions of each phase.

(Cs − Co )
Fl =
(C s − Cl )
 Phase Equilibrium cont.

™ binary eutectic system

- Limited solid solubility

- Tie-lines apply to 2 phase regions
- Invariant reaction at constant temperature
♦3 phase equilibrium

Phase Equilibrium cont.

cool
™ Eutectic L heat S1+S2

cool
™ Eutectoid S1 heat S2+S3

cool
™ Peritectic S1+L heat S2

™ Hypoeutectoid
™ Hypereutectoid
 Chemical Vapor Transport and Condensation

P.D. Yang (USTC 1993. UC Berkeley), Adv. Func. Mater. 12 (2002) 323.

Vapor-Liquid-Solid process to prepare Ge

nanowires
 Vapor-Liquid-Solid (VLS) mechanism
Wagner and Ellis (Bell Telephone Lab)
APL 4 (1964) 89.

Source: SiCl4 (Growth is interrupted as Au is consumed)

Other VSS: TiSi2-catalysed Si; SiOx-catalysed InAs; Au-

catalysed InAs or GaAs

Vapor-Liquid-Solid (VLS) process to prepare

nanowires

To deposit the wires on germanium, the

scientists coated the substrate surface
with a thin layer of gold. Once it was
heated, the gold film broke up into small
particles. These acted as catalysts for
the growth of indium phosphide
nanowires by a vapour-liquid-solid
(VLS) process.

Epitaxially grown GaP nanowires on a

silicon substrate (Philips Research, 2004)
 VLS growth of nonlinear/helical nanowires
(Bandaru et al., J. Appl. Phys. 101, 094307 (2007))

Fig. 1. The nonwetting characteristic of the local

indium catalyst particles on the nano-tube/-fiber
(NT/NF) surface is proposed as an underlying
mechanism for the evolution of nano-coils/-
helices (NC/NH). The concentration of In
influences the coil pitch.
Wetting angle θ =cos−1[(γsv−γsl)/γlv]
In(159º),Sn(156º),Cu(156º),Ge(164º),Al(1
59º); Fe,Co,Ni(<75º).
Catalyst: In isoproxide dissolved in xylene-ferrocene
feed gas mixture
Fig. 2. Transmission electron microscope (TEM)
micrographs of (a) singly wound, or (b) doubly
wound, coiled carbon nanofibers (NF)
synthesized through thermal CVD at high In
concentration (In/Fe ratio>3). (c) Scanning
electron microscope (SEM) micrograph of
nanotube (NT) bundles obtained at lower indium
concentrations (In/Fe ratio<2). (d) High
resolution TEM (HRTEM) of the constituent
tubes in (c) shows the random location of Fe-
based catalyst particles throughout the NT.

Vapor-Solid-Solid (VSS) process to prepare Si

nanowires (Wang et al., Nat. Nanotech. 1 (2006) 186-189)
Ultrahigh vacuum chemical vapour deposition (UHV-CVD) system:10-10 mbar
SiH4 (5%)-Ar(95%) (pSiH4 = 0.25mbar); Substrate: n-type P-doped Si(111)
Al catalyst: ~0.6nm thick, by thermal evaporation, annealed at 580ºC
Si growth: T= 430-490ºC
 Vapor-Solid-Solid (VSS) process to prepare Si
nanowires (Wang et al., Nat. Nanotech. 1 (2006) 186-189)

Effect of growth temperature on the tapering of nanowires

SEM cross-sectional images (tilt 10°) of Si nanowires grown at different temperatures: 490ºC (a)
and 430ºC (b).

Solid-Phase Expitaxy (SPE) Growth: Si

 Phase Transformations

Rate of Phase Transformation

™ Nucleation
™ Growth
Avrami Eqn.
− n
y = 1 − e kt
fraction
transformed time

10 0 0
y (% pearlite)

600癈
% austenite

(ΔT larger)
650癈
• Transformation rate depends on T. 50 50
675癈
(ΔT smaller)
activation energy 10 0
0
1 10 10 2 10 3
1 − time (s)
r= = Ae Q /RT
t 0 .5
 Standard States for Gibbs Free Energy

Parameter Standard State or Condition

Temperature 25oC

Gas 1 atm

Solid Pure Solid

Liquid Pure liquid

Solution 1 M (m/L)

Element* 0

http://webbook.nist.gov/chemistry/

Thermodynamic properties of selected species

SPECIES Δ Go, kcal / mol Δ Ho, kcal /mol

Ca2+(aq) -132.18 -129.77
CaCO3(s), calcite -269.78 -288.45
Ca(OH)2(s), lime -214.7 -235.7
CO2(g) -94.26 -94.05
CO2(aq) -92.31 -98.69
CO32-(aq) -126.2 -161.6
CI-(aq) -31.3 -40.0
CI2(aq) -19.1 -28.9
OCI-(aq) -8.8 -25.6
H+(aq) 0 0
HNO3(aq) -26.6 -25.0
NO3-(aq) -26.6 -49.5
HOCI(aq) -19.1 -28.9
OH-(aq) -37.6 -55.0
O2(aq) 3.9 -3.9
H2O(I) -56.7 -68.3
H2(g) 0 0
O2(g) 0 0
 Chemical thermodynamics
• Consider the reaction
2A + 3B = C + 2D
If we define the extent of reaction by ζ, when the reaction
advances by dζ , the amount of reactants changes by:
dnA = -2 dζ, dnB = -3 dζ, dnC = dζ, dnD = 2 dζ

In general, for a reaction written as ΣνJ J = 0, then dnJ = νJ dζ

• Define chemical potential

ΔRG = ΔRG° +RT lnQ (Q is called the reaction quotient)

• At equilibrium, ΔRG = 0

Chemical Thermodynamics
Temperature dependence of ΔG° for chemical
reactions
Ex.: CaCO3 (s) = CaO(s) + CO 2 (g)
Some data (valid at 25 °C)
ΔH of [CaCO3 (s)] = −1206.9 kJ mol-1 Smo [CaCO3 (s)] = 92.9 J K -1 mol-1
ΔH of [CaO(s)] = −635.1 kJ mol-1 S mo [CaO(s)] = 38.1 J K -1 mol-1
ΔH of [CO 2 (g)] = −393.5 kJ mol-1 S mo [CO 2 (g)] = 213.7 J K -1 mol-1

Calc.:
ΔH o = 1× ΔH of [CaO(s)] + 1× ΔH of [CO 2 ( g )] − 1× ΔH of [CaCO3 (g)]
= 1× −635.1 kJ mol-1 + 1× −393.5 kJ mol-1 − 1× −1206.9 kJ mol-1
= 178.3 kJ mol-1
Chemical Thermodynamics
Temperature dependence of ΔG° for chemical
reactions
CaCO3 (s) = CaO(s) + CO 2 (g)
ΔS o = 1× Smo [CaO(s)] + 1× S mo [CO 2 (g)] − 1× S mo [CaCO3 (g)]
= 1× 38.1 J K -1mol-1 + 1× 213.7 J K -1mol-1 − 1× 92.9 J K -1mol-1
= 158.9 J K -1mol-1
Now
ΔG o = ΔH o − T ⋅ ΔS o
At 25°C (298 K)

ΔG o = 178.3 kJ mol-1 − 298 K × 158.9 J K -1mol-1

= 178.3 kJ mol-1 − 298 K × 0.1589 kJ K -1mol-1

Chemical Thermodynamics
Temperature dependence of ΔG° for chemical
reactions
CaCO3 (s) = CaO(s) + CO 2 (g)
∴ΔG o = 130.9 kJ mol-1.
The large, positive value of ΔG° implies that this reaction has no
tendency to proceed at 25°C under standard state conditions.

We know that: ΔG o = ΔH o − T ⋅ ΔS o
If we assume, as an approximation, that the values of ΔH° and
ΔS° do not change with change in temperature, we could use the
above equation to calculate approximate values of ΔG° at other
temperatures.
Chemical Thermodynamics
Temperature dependence of ΔG° for chemical
reactions
For 1000 K
ΔG o = 178.3 kJ mol-1 − 1000 K × 0.1589 kJ K -1mol-1
= +19 kJ mol-1

The value of ΔG° is still positive, but less so than at 25°C. The
reaction is still not spontaneous under standard state conditions.

For 1200 K
ΔG o = 178.3 kJ mol-1 − 1200 K × 0.1589 kJ K -1mol-1
= −13 kJ mol-1
The value of ΔG° is negative, so we would expect the reaction
to proceed spontaneously at this temperature.

Chemical Thermodynamics
Reversible reactions and the Gibbs function
We have seen that, for a process taking place at constant
temperature and pressure:
The process is thermodynamically favoured if ΔG is -ve,
i.e., if the Gibbs function G decreases during the process.
The process is thermodynamically disfavoured if ΔG is
+ve, i.e., if G increases during the process.
For reactions that can proceed in both directions, the
implication is that:
A process or chemical reaction will proceed spontaneously,
at constant T and p, until a situation is reached when the
Gibbs function of the system is minimized.
Chemical Thermodynamics
Driving non-spontaneous reactions
Consider the following thermal decomposition reaction and assess
its potential for use in the extraction of metallic copper from the
copper ore Cu2S:
Cu 2S(s) → 2Cu(s) + S(s) 1
Ans.:
For this reaction:
ΔH° = +79.4 kJ mol-1 ΔS° = -22.4 J K-1 mol-1.

This is a strongly endothermic reaction, with a negative entropy

change. This seems most unpromising – as confirmed by the
following calculation of ΔG°.

Chemical Thermodynamics
Driving non-spontaneous reactions
ΔG o = ΔH o − T ⋅ ΔS o = +86.2 kJ mol-1 at 25 o C
This reaction is non-spontaneous, and is expected to be non-
spontaneous at all temperatures.
We can however make reaction 1 take place by coupling it with
another reaction:
S(s) + O 2 (g) = SO 2 (g) 2
for which
ΔH° = -296.8 kJ mol-1 ΔS° = 11.1 J K-1 mol-1.
This reaction is exothermic and is accompanied by an increase in
entropy, and therefore should be spontaneous under all conditions
and ΔG° = -300.1 kJ mol-1 at 25°C.
Chemical Thermodynamics
Driving non-spontaneous reactions
If we make reactions 1 and 2 occur together, i.e., if we add
equations 1 and 2 :-
Cu 2S = 2Cu(s) + S(s) ΔG o = +86.2 kJ mol-1 1
S(s) + O 2 (g) = SO 2 (g)
__________________________ Δ G = −300.1 kJ mol
o
__________________
-1
2
Cu 2S + O 2 (g) = 2Cu(s) + SO 2 (g)
__________________________ ΔG o = −213.9 kJ mol-1
__________________ 3

They can be done for any of the thermodynamic state functions. It does not matter
whether a given chemical reaction takes place in one step or in many steps, the
same result must be obtained for the change in a state function.

Upshot is that the combined reaction 3 is very definitely

spontaneous. Reaction 2 can be said to drive reaction 1 .

Chemical Thermodynamics
Driving non-spontaneous reactions
So, by coupling a non-spontaneous reaction with a
spontaneous reaction, we have achieved the desired
conversion of Cu2S into Cu.
The coupling of reactions to cause a non-spontaneous
reaction to occur is very important in biochemical systems.
Many reactions essential to life do not occur spontaneously.
In the human body these reactions can be made to occur by
coupling them with reactions that are spontaneous. The
energy required to drive non-spontaneous processes is
obtained primarily from the metabolism of foods.
Chemical Thermodynamics
Driving non-spontaneous reactions
Ex.:
When glucose is oxidized in the body substantial amounts of energy
are released:
C6 H12 O6 (s) + 6O 2 (g) = 6CO 2 (g) + 6H 2 O(l ) 4
ΔG° = -2870 kJ mol-1 ΔH° = -2816 kJ mol-1.
This energy is employed to drive non-spontaneous reactions.

Reaction 4 does not couple directly with these reactions, Instead

the energy from this reaction is used to make a substance
adenosine triphosphate (ATP) from a substance adenosine
diphosphate (ADP).

Chemical Thermodynamics
Driving non-spontaneous reactions

O O O
R O P O P O P O H ATP
O- O- O-

O O
R O P O P O H
ADP
O- O-
Chemical Thermodynamics
Driving non-spontaneous reactions

Chemical Thermodynamics for Materials Synthesis:

High temperature synthesis tricks
Chemical Thermodynamics for Materials Synthesis:
Chemical Vapor Transport (CVT)

Chemical Thermodynamics for Materials Synthesis:

Chemical Vapor Transport (CVT)
 Chemical kinetics

Generalized Transport laws

Fick’s second law (Diffusion equation)

∂ci
∂t = D∇ 2 ci

Arrhenius relationship of diffusion