Thermal Analysis SSK 4242/3

THE REACTION KINETICS STUDY

• Chemical reactions take place at a certain rate and it is defined
as the rate of change of the amount of the reactant(s)/product(s)
material(s) per unit time
• Parameter(s): pressure; concentration; reaction fraction, α

dn/dt = k · f(n) Arrhenius: rate of reaction is

k : rate constant
f(n) : amount function, n
e.g.: Polymer decay
influenced by temperature
k = A · exp (- E/RT) k = A- E/RT
E : activation energy
A : pre-exponential factor, depends on
the orientation and the structure of the
reactants

dα /dt = k · (1 - α ) The rate of reaction is influenced by:

(a) The amount of reactants, and
(b) The temperature

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The Reaction Kinetics
• Solid state endothermic reaction
A (solid) = B (solid) + C (gas)
- heat is absorbed as the gas and mass
lost
• The extent of reaction, ξ is a
quantity which has the dimension of
the amount of material
nB = nB,0 + νB · ξ
nB : the amount of material B
nB,0 : the selected amount of B,
at t = 0
νB : the stoichiometric number for B
(+ve if B is the reaction product and
–ve if B is the reactant)
Thermal Analysis SSK 4242/3
Three types of chemical reaction
studies by TG, DTA/DSC:
(i) The extent of reaction,
intermediates, and products
(i) Energy or heat involved in the
various levels of reaction
(i) Mechanism and kinetics of
reaction
• For reactions in solution :
- concentration, cB
• For solid state reactions:
- reaction fraction, α
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The Rate of Reaction
Rate = dα /dt = kT · f(α )
kT : rate constant at temperature T
: mathematical expression for α
Examples of relationship between
solid state reaction and α :
(a) Diffusion controlled reaction
dα /dt = kT /2 · (α )
(b) Two dimensional nucleus growth
(Avrami equation)
dα /dt = kT · (1 - α ) · (-ln(1 - α ))1/2
(c) First order reaction: random decay of
an active species
dα /dt = kT · (1 - α )
Thermal Analysis SSK 4242/3
Despite being measured at a fixed
temperature, rate of reaction changes
with time and the value of α
For a reaction in solution or
radiochemical reaction, f(α ) is the
same throughout the sample, but it
may change when the reaction
becomes f′(α ) due to the chemical
change, geometrical change, or a
change in reaction mechanism.
Interpretation of reaction kinetics
equation takes into account the
following:
- the way reaction begins by
nucleation process
- the nucleus growth
- the interaction or interfacial
geometry involved in the reaction
- the reactant decay
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The Reaction Rate Constant
The Rate Constant, k, is strongly influenced
by temperature and sometimes written as
kT.
Arrhenius equation:
kT = A exp(-E/RT)
A = pre-exponential factor
E = activation energy (J/mole)
R = molar gas constant (8.314 J/(K mole)
The reaction mechanism may change
during the reaction which can influence
the value of E.
Thermal Analysis SSK 4242/3
Temperature Control
In a non-isothermal experiment,
temperature is controlled according
to a linear temperature rise, β
K/min, and at the time t:
Tt = T0 + β · t
However, in the real situation an
endothermic or exothermic process
will change the actual temperature
and the equation is modified as
follows
Tt = T0 + β · t + s(t)
where s(t) is the difference between
the sample temperature and the
programmed temperature.
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Reaction Kinetics and DSC Curves
• The rate of a chemical reaction and a
physical change can be influenced by
temperature and ΔH.
• Hence, a relationship exists between
- the ΔH and the DSC peak area
- the rate of reaction and the rate of
heat flow, ΔP
• Heat capacity change
- estimated by the change in the
baseline of the DSC curve
- independent of the rate of reaction
but dependent on the materials
present in the sample
• Control of temperature gradient in
the sample
- use as small sample size as possible
- instrumental control system.
Thermal Analysis SSK 4242/3
DTA/DSC Peak Thermograms
• The peaks are divided into several
fractions, each of which represents the
reaction fraction α that has taken
place, respectively.
• Kinetics study of a single step
reaction, example:
a) Decomposition of free radical initiator
of azobisisobutyronitrile (AIBN) – by
DSC method:
4 – 32 K/min will produce data that is
suitable for first order kinetics and the
activation energy of 125 kJ/mol.
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 Thermal Analysis SSK 4242/3

b) Measurement of the rate of

polymer crystallization
using the partial area
by
to
The Relationship of DSC
determine the percantage
the polymer crystallized.
of
Curve and α
The results are normally The DSC curve for an exothermic reaction
compatible with the Avrami showing the measurement of partial peak area
equation

[-ln(1 - α ]1/ n = kt

where
α : the final crystallinity at the
time t

n : depends on the crystal growth

mechanism, e.g. n = 3 for
spherical growth

Figure 8.1
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ASTM E698-79 Standard Method for

The Evaluation of Thermal Hazards

Evaluation of thermal
hazards by the kinetics data An isothermal DSC curve for polymer
is a standard method ASTM crystallization
E698-79.
Figure 8.2

The sample is repeatedly heated for several times at various heating rates, β , and
the peak temperature of the thermogram is recorded, Tmax . The plot of ln(β )
versus 1/ Tmax produces a straight line with the slope of E/R.

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 Thermal Analysis SSK 4242/3
The Application of DSC/DTA On The
Organic and Complex Compounds
Calcium oxalate monohydrate (CaC2O4 · H2O)
The DTA curve for calcium
(b) oxalate monohydrate:
(a) in nitrogen,
(b) in the air.
Sample: 10 mg, 10 K/min
CO + O2 → CO2

(a)
Decomposition
of calcium
Oxalate carbonate
Hydration water decomposition

Figure 8.3 Lecture 8 Application DTA&DSC01 8

 Thermal Analysis SSK 4242/3

Copper Sulphate Pentahydrate (CuSO4 · 5H2O)

(a)
The DTA curve for copper sulphate
III (b) pentahydrate:
I II (a) unsealed plate
(b) sealed plate and pin-holed
Sample: 6 mg of powdered crystal,
10 K/min, air-flow.
Figure 8.4
Sample decomposition:
CuSO4 = CuO + SO2 + ½ O2

I CuSO4 · 5H2O = CuSO4 · 3H2O + 2H2O ∆ H (373 K) = 100 kJ/mole

II CuSO4 · 3H2O = CuSO4 · H2O + 2H2O ∆ H (400 K) = 104 kJ/mole
III CuSO4 · H2O = CuSO4 + 2H2O ∆ H (510 K) = 72 kJ/mole

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 Thermal Analysis SSK 4242/3

Ordinary Portland Cement (OPC)

• OPC = Ordinary Portland Cement contains largely calcium sylicates
because it is made by heating clay (alumino-sylicate) and calcium
carbonate
• When used, cement is mixed with water that will hydrate the sylicates,
and it is gradually transformed into a good cement material that produces
the final strength in several months.

dehydration
Quartz transition: 573 oC

Figure 8.5: DTA curve for a sample of Portland Cement concrete (50 mg, 20
K/min, nitrogen) (Source: H_F 3.38)

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 Thermal Analysis SSK 4242/3

High Alumina Cement HAC

• The high alumina cement (HAC) is made from bauxite and lime
stone to produce a calcium aluminate mixture.

• When mixed with water, HAC produces cement at a faster rate

than the OPC, hence speeds up the construction process, but
under certain circumstances the HAC concrete beams tend to
break and result in accidents.

• During the hardening process CaO⋅ Al2O3⋅ 10H2O is formed, but this is not the
most stable hydrate and will slowly be converted to a more stable compounds
such as hexahydrate, hydrated alumina or gibbsite.
3CaO⋅ Al2O3⋅ 10H2O (or C3AH6) and Al2O3⋅ 3H2O (or AH3)
3(CaO⋅ Al2O3⋅ 10H2O) = 3CaO⋅ Al2O3⋅ 6H2O + Al2O3⋅ 3H2O + 18H2O

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 Thermal Analysis SSK 4242/3

The Degree of
conversion (Dc)
• Conversion reaction weakens the (a)
concrete because the reaction
product is denser than the original
concrete and the reacting structure
becomes porous, especially if the
conversion process takes place
rapidly.
• Decahydrate, hexahydrate and
gibbsite lost their water molecules (b)
when heated as shown in Figure
8.6.
• Sampling by drilling of the
concrete should be carried out Figure 8.6: DTA curves for standard HAC that has
carefully conversion of 50 % (a) and 70 % (b) (source: H_F 3.39)

• Avoid gypsum and plaster, remove the drilling metal pieces

• 10 – 100 mg of sample is analysed at 10 – 30 K/min, nitrogen atmosphere
• The degree of conversion is determined from the height of the peak

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 Thermal Analysis SSK 4242/3

The Determination of Dc
100·Amount of AH3
Dc =
(Amount of AH3 + Amount of CAH10 )

or

100·a·(Peak height AH3)

Dc =
(a·Peak height AH3 + b · Peak height CAH10 )

or
100·(Peak Height AH3)
Dc =
(Peak height AH3 + Peak height CAH10 )

Where a and b are calibration constants and K = b/a Figure 8.6: DTA curves for standard HAC that has
conversion of 50 % (a) and 70 % (b) (source: H_F 3.39)

• Avoid gypsum and plaster, remove the drilling metal pieces

• 10 – 100 mg of sample is analysed at 10 – 30 K/min, nitrogen atmosphere
• The degree of conversion is determined from the height of the peak

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 Thermal Analysis SSK 4242/3

Calculation for the Determination of Dc

The calibration constant K is determined by analysing a standard material

that has 50 % dan 70 % conversion. For the 50 % conversion, the peak
height AH3 is 3.5 cm, while the peak height for CAH10 is 3.7 cm.

Hence, 50 % = 100 x 3.5/(3.5 + K x 3.7)

and K = 0.95

For the unknown sample HAC, the peak height HAC3 is 4.4 cm and for
the peak CAH10 is 2.6 cm

Therefore Dc = 100 x 4.4/(4.4 + 0.95 x 2.6)

= 64 ± 5 % conversion

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The Application of
DSC/DTA to the Clays
and Minerals

Peaks
- Single mineral components
e.g. quartz, undergoes phase
transition
- Hydrated minerals
- Dehydration peaks indicate
hydroxyl
- Carbonate minerals lost CO2

Figure 8.7: DTA curve for

several types of minerals
(source: H_F 3.40)

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Kaolinite Formation of mullite crystal

3Al2O3·2SiO2

Hydration water
Dehydroxylation

Figure 8.8: DTA curve for kaolinite

(Source: H_F 3.41)
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Figure 8.9
Borate
A complex mineral M2B6O11 ·xH2O

Some contains anion that is bound to chained

bondong and not easily dissociated except at
higher tempertatures (source: H_F 3.42(b))

Some contains discrete ions that losses water molecules at a

temperature below 250 oC (Source: H_F 3.42(a))

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Synthesis of compounds at Thermal Analysis SSK 4242/3

higher temperature
High temperature inorganic reactions
produce many new compounds useful for
a) BaCO3 the electronics industry

Example: heating of a
BaCO3 and Fe2O3 mixture

b) Iron oxide: α Fe2O3

Two levels of crystal transition

Figure 8.10

Barium hexaferite: BaFe12 O19

c) BaCO3 : 6Fe2O3 mixture - Useful as a solid magnet in
the induction component

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 Thermal Analysis SSK 4242/3

Oxidation Decay of Polymers

• Polymer/oil decays when heated in an
oxidizing atmosphere
• The sample is heated in N2 until 200 oC
• The atmosphere is changed to oxygen and
the temperature maintained at 200 oC
• The time required for the sample to achieve
the oxidation process is recorded, or
• The polymer is heated in O2 and the
temperature where the oxidation occurs is
recorded.

Figure 8.11: DSC curve for the oxidation of

polyethylene (PE). The dotted line indicates the
change of atmosphere N2 → O2.
(a) DSC scan for the PE layer, 10 K/min, oxidation
onset temperature = 220 oC
(b) DSC isotherm for the PE layer at 200 oC; onset
time = 35 min. H_F 3.46
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Polymer Curing
• Polymerization: reaction 1st heating
between small molecules to
produce bigger molecules with
different properties
• For unsaturated molecules, such
as styrene and vinyl chloride,
∆ H = -100 kJ/mole (exothermic)
2nd heating
a) Reaction takes place at low temperature
but becomes faster when heated above
100 oC. The initial reaction of Tg is
followed by an exothermic curing
reaction.
b) Re-heating of the cured sample may
produce higher temperature of Tg .
Figure 8.12
O OH

R-NH2 + CH2----CH-R’ → R-NH-CH2-CH-R’

→ R-N(CH2-CHOH-R’)2
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 Thermal Analysis SSK 4242/3

Protein Denaturation
Colagen (single material)
800 mg, colagen solution 0.3
%, sealed container, 0.5 K/min Proteins (e.g. colagen) can exist as long
molecules such as fibre, or round or
compact molecules such as insulin.

Protein structure:
- folded
- scrolled
- sheet
- helix and super-helix
(helix in helix)

The structures are destroyed

when heated or denaturized
under an extreme pH.
Complex samples These changes are endothermic.
of animal muscle
protein 850 mg, sealed container, 0.2 K/min

Figure 8.13
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Polymer Decay
Figure 8.14 shows DTA curves for the PVC
decomposition of poly(vinyl chloride), PVC
and polypropylene (PP) (Source: H_F 3.49 & 3. 50)

PVC: PVC powder shows a small glass

transition at 80 oC, followed by a small
endothermic process at 300 oC, and
immediately followed by a large exothermic
at 550 oC:
- decay process with a loss of HCl
- volatile material
- oxidation of the released carbon PP

PP: decomposed in a single step process

and the product is easily oxidised. Hence, the
endothermic process of melting at 80 oC is
followed by a large exothermic oxidation
peak.

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