You are on page 1of 22

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


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

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


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

Lecture 8 Application DTA&DSC01 1


Thermal Analysis SSK 4242/3

The Reaction Kinetics


Three types of chemical reaction
• Solid state endothermic reaction studies by TG, DTA/DSC:
(i) The extent of reaction,
A (solid) = B (solid) + C (gas) intermediates, and products
- heat is absorbed as the gas and mass (i) Energy or heat involved in the
lost
various levels of reaction

• The extent of reaction, ξ is a (i) Mechanism and kinetics of


quantity which has the dimension of reaction
the amount of material
nB = nB,0 + νB · ξ • For reactions in solution :
nB : the amount of material B - concentration, cB
nB,0 : the selected amount of B,
at t = 0
• For solid state reactions:
νB : the stoichiometric number for B - reaction fraction, α
(+ve if B is the reaction product and
–ve if B is the reactant)
Lecture 8 Application DTA&DSC01 2
Thermal Analysis SSK 4242/3

The Rate of Reaction Despite being measured at a fixed


temperature, rate of reaction changes
with time and the value of α
Rate = dα /dt = kT · f(α ) For a reaction in solution or
radiochemical reaction, f(α ) is the
kT : rate constant at temperature T
same throughout the sample, but it
: mathematical expression for α may change when the reaction
becomes f′(α ) due to the chemical
change, geometrical change, or a
Examples of relationship between
change in reaction mechanism.
solid state reaction and α :
Interpretation of reaction kinetics
(a) Diffusion controlled reaction
equation takes into account the
dα /dt = kT /2 · (α )
following:
(b) Two dimensional nucleus growth - the way reaction begins by
(Avrami equation) nucleation process
- the nucleus growth
dα /dt = kT · (1 - α ) · (-ln(1 - α ))1/2
- the interaction or interfacial
geometry involved in the reaction
(c) First order reaction: random decay of - the reactant decay
an active species
dα /dt = kT · (1 - α )
Lecture 8 Application DTA&DSC01 3
Thermal Analysis SSK 4242/3

The Reaction Rate Constant


The Rate Constant, k, is strongly influenced Temperature Control
by temperature and sometimes written as In a non-isothermal experiment,
kT. temperature is controlled according
to a linear temperature rise, β
Arrhenius equation: K/min, and at the time t:

kT = A exp(-E/RT) Tt = T0 + β · t
However, in the real situation an
A = pre-exponential factor
endothermic or exothermic process
E = activation energy (J/mole) will change the actual temperature
R = molar gas constant (8.314 J/(K mole) and the equation is modified as
follows
The reaction mechanism may change
during the reaction which can influence Tt = T0 + β · t + s(t)
the value of E.
where s(t) is the difference between
the sample temperature and the
programmed temperature.

Lecture 8 Application DTA&DSC01 4


Thermal Analysis SSK 4242/3

Reaction Kinetics and DSC Curves


• The rate of a chemical reaction and a
physical change can be influenced by
DTA/DSC Peak Thermograms
temperature and ΔH.
• Hence, a relationship exists between • The peaks are divided into several
- the ΔH and the DSC peak area fractions, each of which represents the
- the rate of reaction and the rate of reaction fraction α that has taken
heat flow, ΔP place, respectively.

• Heat capacity change • Kinetics study of a single step


- estimated by the change in the reaction, example:
baseline of the DSC curve a) Decomposition of free radical initiator
- independent of the rate of reaction of azobisisobutyronitrile (AIBN) – by
but dependent on the materials DSC method:
present in the sample
4 – 32 K/min will produce data that is
• Control of temperature gradient in suitable for first order kinetics and the
the sample activation energy of 125 kJ/mol.
- use as small sample size as possible
- instrumental control system.

Lecture 8 Application DTA&DSC01 5


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
Lecture 8 Application DTA&DSC01 6
Thermal Analysis SSK 4242/3

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.

Lecture 8 Application DTA&DSC01 7


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

Lecture 8 Application DTA&DSC01 9


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)

Lecture 8 Application DTA&DSC01 10


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

Lecture 8 Application DTA&DSC01 11


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

Lecture 8 Application DTA&DSC01 12


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

Lecture 8 Application DTA&DSC01 13


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

Lecture 8 Application DTA&DSC01 14


Thermal Analysis SSK 4242/3

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)

Lecture 8 Application DTA&DSC01 15


Thermal Analysis SSK 4242/3

Kaolinite Formation of mullite crystal


3Al2O3·2SiO2

Hydration water
Dehydroxylation

Figure 8.8: DTA curve for kaolinite


(Source: H_F 3.41)
Lecture 8 Application DTA&DSC01 16
Thermal Analysis SSK 4242/3

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))

Lecture 8 Application DTA&DSC01 17


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

Lecture 8 Application DTA&DSC01 18


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
Lecture 8 Application DTA&DSC01 19
Thermal Analysis SSK 4242/3

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
Lecture 8 Application DTA&DSC01 20
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
Lecture 8 Application DTA&DSC01 21
Thermal Analysis SSK 4242/3

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.

Lecture 8 Application DTA&DSC01 22