Analisa Termal

Teknik Analisa Termal

Sejumlah teknik pengukuran dimana sifat-sifat fisik diukur sebagai fungsi dari
suhu, dimana sampel dikenakan proses pemanasan atau pendinginan tertentu.

Differential Thermal Analysis (DTA)

• Perbedaan suhu antara sampel dengan material standar yang inert, T = TS - TR,
diukur saat keduanya diberi perlakuan panas tertentu.

Differential Scanning Calorimetry (DSC)

• Sampel dan standar dijaga pada suhu yang sama, bahkan selama terjadi perubahan-
perubahan termal tertentu pada sampel.

• Variabel yang diukur adalah besarnya energi yang diperlukan untuk menjaga
perbedaan suhu sampel dan standar sama dengan nol, d q/dt.

Thermogravimetric Analysis (TGA)

• Pengukuran dilakukan pada perubahan massa sampel akibat pemanasan.

 Prinsip-prinsip dasar analisa termal
Instrumentasi modern yang digunakan pada analisa termal biasanya terdiri dari
empat bagian:

1)Sample/sample holder

2)Sensor untuk mendeteksi/mengukur sifat-sifat tertentu sampel dan suhu.

3)Pengaturan yang memungkinkan paremeter-parameter eksperimen dapat dikontrol.

4)Komputer yang memungkinkan pengumpulan dan pemrosesan data.

DTA power compensated DSC heat flux DSC

 Differential Thermal Analysis

sample holder
alumina block
• sample and reference cells (Al) heating
coil

sensors
sample reference
• Pt/Rh atau chromel/alumel thermocouples pan pan

• Satu untuk sampel dan satu untuk reference

• Dihubungkan dengan pengontrol suhu
diferensial
inert gas
vacuum

furnace

• alumina block berisi sampel dan reference Pt/Rh or chromel/alumel

thermocouples
temperature controller

• Mengontrol program suhu dan atmosfer

furnace
 Differential Thermal Analysis

keuntungan:

• Instrumen dapat digunakan pada suhu yang

sangat tinggi

• Instrumen sangat sensitif

• Volume dan bentuk crucible fleksibel

• Transisi atau suhu reaksi yang karakteristik

dapat ditentukan dengan akurat,

DTA
kelemahan:

• Ketidakpastian estimasi panas bagi reaksi,

transisi dan fusi sekitar 20-50%
 Differential Scanning Calorimetry
• DSC differs fundamentally from DTA in that the sample and reference are both
maintained at the temperature predetermined by the program.

• during a thermal event in the sample, the system will transfer heat to or from the
sample pan to maintain the same temperature in reference and sample pans

• two basic types of DSC instruments: power compensation and heat-flux

power compensation DSC heat flux DSC

 Power Compensation DSC
individual
heaters
controller P

sample reference
pan pan

sample holder

• Al or Pt pans inert gas inert gas

vacuum vacuum

sensors thermocouple T=0

• Pt resistance thermocouples
• separate sensors and heaters for the sample and reference

furnace

• separate blocks for sample and reference cells

temperature controller

• differential thermal power is supplied to the heaters to maintain the temperature

of the sample and reference at the program value
 Sample Preparation

• accurately-weigh samples (~3-20 mg)

• small sample pans (0.1 mL) of inert or treated metals (Al, Pt, Ni, etc.)

• several pan configurations, e.g., open , pinhole, or hermetically-sealed pans

• the same material and configuration should be used for the sample and the
reference

• material should completely cover the bottom of the pan to ensure good
thermal contact

• avoid overfilling the pan to minimize thermal lag from the bulk of the
material to the sensor

* small sample masses and

low heating rates increase
resolution, but at the
expense of sensitivity
Al Pt alumina Ni Cu quartz
 Heat Flux DSC
heating
coil

sample holder sample reference

pan pan

• sample and reference are connected by constantan

a low-resistance heat flow path chromel/alumel
wires
• Al or Pt pans placed on constantan disc
inert gas
vacuum thermocouples

sensors
chromel wafer

• chromel®-constantan area thermocouples (differential heat flow)

• chromel®-alumel thermocouples (sample temperature)

furnace

• one block for both sample and reference cells

temperature controller

• the temperature difference between the sample and reference is converted to

differential thermal power, d q/dt, which is supplied to the heaters to maintain the
temperature of the sample and reference at the program value
 Modulated DSC (MDSC)

• introduced in 1993; “heat flux” design

Modulated DSC Heating Profile
• sinusoidal (or square-wave or sawtooth)
modulation is superimposed on the
underlying heating ramp

• total heat flow signal contains all of

the thermal transitions of standard
DSC

• Fourier Transformation analysis is used

to separate the total heat flow into its
two components:

heat capacity (reversing heat flow) kinetic (non-reversing heat flow)

glass transition crystallization

melting decomposition
evaporation
enthalpic relaxation
cure
 Analysis of Heat-Flow in Heat Flux DSC
• temperature difference may be deduced by considering the heat flow paths in the
DSC system
heating block
Tfurnace

TR TS
temperature

TRP
TSP
thermocouple is not in physical
TR TL contact with sample
reference
TS
sample

• thermal resistances of a heat-flux system change with temperature

• the measured temperature difference is not equal to the difference in temperature

between the sample and the reference

Texp ≠ TS – TR
 DSC Calibration

baseline

• evaluation of the thermal resistance of the

sample and reference sensors

• measurements over the temperature range

of interest

2-step process

• the temperature difference of two

empty crucibles is measured

• the thermal response is then acquired

for a standard material, usually
sapphire, on both the sample and
reference platforms

• amplified DSC signal is automatically varied with temperature to maintain a constant

calorimetric sensitivity with temperature
 DSC Calibration
temperature

• goal is to match the melting onset temperatures indicated by the furnace

thermocouple readouts to the known melting points of standards analyzed by DSC

• should be calibrated as close to the desired temperature range as possible

heat flow

• use of calibration standards of known heat capacity, such as sapphire, slow accurate
heating rates (0.5–2.0 °C/min), and similar sample and reference pan weights

calibrants metals
• In 156.6 °C; 28.45 J/g
• high purity • Sn 231.9 °C
• accurately known enthalpies • Al 660.4 °C
• thermally stable inorganics
• light stable (h ) • KNO3 128.7 °C
• nonhygroscopic • KClO4 299.4 °C
• unreactive (pan, atmosphere) organics
• polystyrene 105 °C
• benzoic acid 122.3 °C; 147.3 J/g
• anthracene 216 °C; 161.9 J/g
 Thermogravimetric Analysis (TGA)

• thermobalance allows for monitoring

sample weight as a function of
temperature

• two most common instrument types

reflection

null

• weight calibration using calibrated

weights Sample: Calcium Oxalate
Size: 7.9730 mg TGA
File: Y:\Data\TGA\Calcium oxalate\032304.001
Operator: SLT
Run Date: 23-Mar-04 14:57
Instrument: 2950 TGA HR V5.4A
120

• temperature calibration based on

ferromagnetic transition of Curie point
100
12.15%

standards (e.g., Ni) 80 19.32%

Weight (%)
60

• larger sample masses, lower temperature

29.99%

gradients, and higher purge rates 40

minimize undesirable buoyancy effects 20

0 20 40 60 80 100 120 140 160
Time (min) Universal V3.7A TA Instruments

TG curve of calcium oxalate

Typical Features of a DSC Trace for a Polymorphic System

endothermic events

melting
sublimation
solid-solid transitions
desolvation
chemical reactions

exothermic events

crystallization
solid-solid transitions
sulphapyridine decomposition
chemical reactions

baseline shifts

glass transition
Thermal Methods in the Study of Polymorphs and Solvates
polymorph screening/identification

thermal stability
• melting
1.0

• crystallization 0.5

• solid-state transformations
• desolvation 0.0

• glass transition

Heat Flow (W/g)

-0.5

• sublimation
• decomposition -1.0

heat flow
-1.5
––––––– Form II
Form
––––––– Form IIII

• heat of fusion
Form
––––––– Variable
Form III Hydrate
––––––– Dihydrate
-2.0
––––––– Acetic acid solvate

• heat of transition
• heat capacity -2.5
0 50 100 150 200 250 300 350
Exo Up Temperature (°C)

mixture analysis
• chemical purity
• physical purity (crystal forms, crystallinity)

phase diagrams
• eutectic formation (interactions with other molecules)
 Sample: INDIUM CRIMPED PAN CHECK File: C:...\10C per min crimped\DSC010920A.3

Definition of Transition Temperature

Size: 7.6300 mg DSC Operator: Ron Vansickle
Method: indium Run Date: 20-Sep-01 09:13
Comment: P/N 56S-107 Instrument: 2920 MDSC V2.6A
0.5

156.50°C
28.87J/g
0.0

extrapolated
-0.5 onset temperature
Heat Flow (W/g)

-1.0

-1.5

peak melting
-2.0 temperature

157.81°C

-2.5
140 145 150 155 160 165 170 175
Exo Up Temperature (°C) Universal V3.3B TA Instruments
 Melting Processes by DSC

pure substances

• linear melting curve

• melting point defined impure substances

by onset temperature eutectic
melt • concave melting curve

• melting characterized
at peak maxima

• eutectic impurities
may produce a second
melting with decomposition peak

• exothermic

• endothermic
 Glass Transitions
• second-order transition characterized by
change in heat capacity (no heat absorbed
or evolved)

• transition from a disordered solid to a

liquid

• appears as a step (endothermic direction)

in the DSC curve

• a gradual volume or enthalpy change may occur, producing an endothermic peak

superimposed on the glass transition
 Sample: INDIUM CRIMPED PAN CHECK File: C:...\10C per min crimped\DSC010920A.3

Enthalpy of Fusion
Size: 7.6300 mg DSC Operator: Ron Vansickle
Method: indium Run Date: 20-Sep-01 09:13
Comment: P/N 56S-107 Instrument: 2920 MDSC V2.6A
0.5

156.50°C
28.87J/g
0.0

-0.5
Heat Flow (W/g)

-1.0

-1.5

-2.0

157.81°C

-2.5
140 145 150 155 160 165 170 175
Exo Up Temperature (°C) Universal V3.3B TA Instruments
 Burger’s Rules for Polymorphic Transitions
enantiotropy monotropy
endothermic

endothermic
Heat of Transition Rule
• endo-/exothermic solid-solid transition • exothermic solid-solid transition

Heat of Fusion Rule

• higher melting form; lower Hf • higher melting form; higher Hf
 Enthalpy of Fusion by DSC

single (well-defined) melting endotherm

• area under peak

• minimal decomposition/sublimation
• readily measured for high melting polymorph
• can be measured for low melting polymorph

multiple thermal events leading to stable melt

• solid-solid transitions (A to B) from which the transition enthalpy ( HTR) can be

measured*

HfA = HfB - HTR

crystallization of stable form (B) from melt of (A)

HfA = area under all peaks from B to the stable melt

* assumes negligible heat capacity difference between polymorphs over temperatures of interest
 Purity by DSC

• eutectic impurities lower the melting

point of a eutectic system

• purity determination by DSC based on

Van’t Hoff equation

RTo2 . 1 97%
Tm = To -
Ho f
99%
• applies to dilute solutions, i.e., nearly
pure substances (purity ≥98%)
benzoic acid 99.9%

• 1-3 mg samples in hermetically-sealed

pans are recommended
melting endotherms as a function of purity.
• polymorphism interferes with purity
determination, especially when a
transition occurs in the middle of the
melting peak

Plato, C.; Glasgow, Jr., A.R. Anal. Chem., 1969, 41(2), 330-336.
 Effect of Heating Rate

• many transitions (evaporation, crystallization,

decomposition, etc.) are kinetic events

… they will shift to higher temperature when

heated at a higher rate

• the total heat flow increases linearly with

heating rate due to the heat capacity of the
sample

… increasing the scanning rate increases

sensitivity, while decreasing the scanning
rate increases resolution

• to obtain thermal event temperatures close

to the true thermodynamic value, slow
scanning rates (e.g., 1–5 K/min) should be
used DSC traces of a low melting polymorph collected
at four different heating rates. (Burger, 1975)
 Effect of Phase Impurities
• lots A and B of lower melting polymorph (identical by XRD) are different by DSC

Lot A - pure
2046742
FILE# 022511DSC.1

-1
Heat Flow (W/g)

-2

Lot B - seeds
2046742
FILE# 022458 DSC.1 Form II ?
-3

-4

-5
80 130 180 230 280
Exo Up Temperature (°C) Universal V3.3B TA Instruments

• Lot A: pure low melting polymorph – melting observed

• Lot B: seeds of high melting polymorph induce solid-state transition below the melting
temperature of the low melting polymorph
 Polymorph Characterization: Variable Melting Point
• lots A and B of lower melting polymorph (identical by XRD) appear to have a “variable”
melting point
0.1

-0.1

Lot A
-0.3
Heat Flow (W/g)

-0.5

Lot B
-0.7

-0.9

DSC010622b.1 483518 HCL (POLYMORPH 1)

DSC010622d.1 483518 HCL

-1.1
110 120 130 140 150 160 170 180
Exo Up Temperature (°C) Universal V3.3B TA Instruments

• although melting usually happens at a fixed temperature, solid-solid transition

temperatures can vary greatly owing to the sluggishness of solid-state processes
 Polymorph Characterization: Variable Melting Point

• the low temperature endotherm was predominantly non-reversing, suggestive of a

solid-solid transition

• small reversing component discernable on close inspection of endothermic conversions

occurring at the higher temperatures, i.e., near the melting point

0.00 0.2

reversing heat flow non-reversing heat flow

Reversing (heat flow component) Non-reversing (heat flow component)

-0.05

-0.10 0.0

-0.15 Lot A Lot A

Nonrev Heat Flow (W/g)

Rev Heat Flow (W/g)

-0.20 -0.2

-0.25

-0.30
Lot B -0.4
Lot B
-0.35

-0.40 -0.6

-0.45 DSC010622b.1 483518 HCL (POLYMORPH 1) DSC010622b.1 483518 HCL (POLYMORPH 1)

DSC010622d.1 483518 HCL DSC010622d.1 483518 HCL

-0.50 -0.8
110 120 130 140 150 160 170 180 110 120 130 140 150 160 170 180
Exo Up Temperature (°C) Universal V3.3B TA Instruments
Exo Up Temperature (°C) Universal V3.3B TA Instruments

• the “variable” melting point was related to the large stability difference between the
two polymorphs; the system was driven to undergo both melting and solid-state
conversion to the higher melting form
 Polymorph Stability from Melting and Eutectic Melting Data

• polymorph stability predicted from pure melting data near the melting temperatures

(G1-G2)(Tm1) = Hm2(Tm2-Tm1)/Tm2 0.4 GON-GY, kJ/mole

0.2
(G1-G2)(Tm2) = Hm1(Tm2-Tm1)/Tm1 0 Y

sdf
Tt
-0.2 ON
• eutectic melting method developed
to establish thermodynamic stability -0.4
eutectic melting melting
of polymorph pairs over larger
temperature range

DSC Signal
Y
ON ON Y
(b) ON
ON
Y ON Y
TmA Tm1 Y
+benzil pure forms
A P1 Tm2 +thymol +azobenzene +acetanilide
40 60 80 100 120
P2 T, oC

TmRC
RC (G1-G2)(Te1) = Hme2(Te2-Te1)/(xe2Te2)
Te2
(G1-G2)(Te2) = Hme1(Te2-Te1)/(xe1Te1)
Te1

1 0
xe2 xe1 x 1 Yu, L. J. Pharm. Sci., 1995, 84(8), 966-974.
Yu, L. J. Am. Chem. Soc, 2000, 122, 585-591.
 “Hyphenated” Techniques

• thermal techniques alone are insufficient to prove the existence of

polymorphs and solvates

• other techniques should be used, e.g., microscopy, diffraction, and

spectroscopy

• development of “hyphenated” techniques for simultaneous analysis

Sample: SODIUM TARTRATE (ALDRICH) File: C:\TA\Data\Sdtcal\2004\TGA040105A.5
Size: 6.1176 mg TGA-DTA Operator: Ron Vansickle
Method: 25C TO 300 Run Date: 6-Jan-04 12:09
Comment: LOT# 22411A0 Instrument: 2960 SDT V3.0F

TG-DTA 120

15.55%
4.2

(0.9513mg)

24.80°C

TG-DSC
3.2
100.0%
80

Temperature Difference (µV/mg)

179.95°C
84.45%
2.2

TG-FTIR Weight (%)

40 1.2

evolved gas analysis 0.2

TG-MS (EGA) 0

-0.8

-40 -1.8
20 70 120 170 220 270
Exo Up Temperature (°C) Universal V3.3B TA Instruments

TG-DTA trace of sodium tartrate

 Best Practices of Thermal Analysis

• small sample size

• good thermal contact between the sample and the temperature-sensing

device

• proper sample encapsulation

• starting temperature well below expected transition temperature

• slow scanning speeds

• proper instrument calibration

• use purge gas (N2 or He) to remove corrosive off-gases

• avoid decomposition in the DSC

 Reversing and Non-Reversing Contributions
to Total DSC Heat Flow

total heat flow

resulting from dQ/dt = Cp . dT/dt + f(t,T)
average heating rate

reversing signal non-reversing signal

heat flow resulting from (kinetic component)
sinusoidal temperature modulation
(heat capacity component)

* whereas solid-solid transitions are generally too sluggish to be reversing at

the time scale of the measurement, melting has a moderately strong
reversing component
 Recognizing Artifacts

mechanical
sample pan cool air entry
sample topples shock of
distortion shifting
over in pan measuring cell into cell
of Al pan

sensor
contamination

RT changes intermittant
electrical effects, closing of hole
power spikes, etc. in pan lid
burst of
pan lid