Aim: To perform thermo-gravimetric analysis of calcium oxalate.

Apparatus: thermal analysis set up, Al2O3 crucibles, spatula, tweezers, gloves, weighing
machine.

Chemicals: Calcium Oxalate (CaC2O4 + 1 H2O).

Principle/ Theory:
Thermal Analysis

Characterization techniques for the evaluation and estimation of properties of materials

can be divided into two categories, 1) Destructive techniques and 2) Non destructive techniques.

In destructive technique the whole or part of the sample under testing is destroyed.
Examples: Chemical analysis; thermal analysis; mechanical testing like ball milling, tensile and
compressive strength measurement, scratch testing, frictional coefficient measurement, etc.

In non-destructive technique the sample is preserved and is not destroyed during the
characterization process. Example: Infra red spectroscopy, Uv-visible spectroscopy, X-ray
photoelectron spectroscopy, Raman spectroscopy, etc.

Thermal analysis helps in gaining information regarding the sample. The formal
definition of Thermal analysis as given by the International Confederation for Thermal Analysis
and Calorimetry) and Japanese Industrial Standards (JIS) is

“A group of techniques in which a property of the sample is monitored against time or

temperature while the temperature of the sample in a specific atmosphere is programmed.”

Thermo-gravimetric analysis (TGA)

Thermo-gravimetric analysis is a analytical thermal technique that is performed on a

sample for determining the weight change as a function of temperature and time. Some
instruments are capable of measuring temperature difference of the specimen with respect to a
reference sample.

For the analysis to be carried out in effective way it is necessary to have a high degree of
precision in the measurement of weight, temperature and temperature change. As many weight
loss curves look similar, the weight loss curve may require transformation before results may be
interpreted. A derivative weight loss curve can be used to tell the point at which weight loss is
most apparent.

A simplified explanation of a TGA sample evaluation may be described as

follows. A sample is placed into a tared TGA sample pan which is attached to a sensitive
microbalance assembly. The sample holder portion of the TGA balance assembly is subsequently
placed into a high temperature furnace. The balance assembly measures the initial sample weight
at room temperature and then continuously monitors changes in sample weight (losses or gains)
as heat is applied to the sample. TGA tests may be run in a heating mode at some controlled
heating rate, or isothermally. Typical weight loss profiles are analyzed for the amount or percent
of weight loss at any given temperature, the amount or percent of noncombusted residue at some
final temperature, and the temperatures of various sample degradation processes.

Measuring Signal:

Temperature dependence

M = m(T) or ΔM = m(T) - mo

Time dependence

M = m(t) or ΔM = m(t) - m(to)

Where

m: sample mass

mo: original sample mass

T: temperature

t: time

to: start of measurement

Procedure:
A) Zero baseline curve:

1. Switch the balance to ON

2. Open the furnace “plug-in” on the top.

3. Carefully remove the sample crucible.

• Clean the crucible or replace it if the old sample can not be cleaned from the crucible.

• Inspect the Al2O3 reference material. If it is contaminated replace with new Al 2O3.

• Place equal amounts of Al2O3 in the reference and sample crucibles.

• The normal amount is 1/3 full (max. 150 mg for sample and reference).
 • Close the “plug-in” on the furnace top.

4. Start the software STA data collection software using the desktop icon.

a) Select “DATA ACQUISITION”, “TYPE”, “ZERO LINE TG+DTA”.

b) Select “DATA ACQUISITION”, “SETTINGS…”

c) Enter the data collection information . The data collection termination is control by
the Duration and End Temp. Value. Once either value is reached the data collection
will be terminated. Always select a time or temperature higher than the final data
point needed. Click “OK” to complete settings

d) Select “CONTROLLER”, “TEMPERATURE PROFILE…”

e) Enter the desired heating rate to the maximum temperature.

f) Select “CONTROLLER”, “CURRENT VALUES”

g) Check the current furnace and sample temperature. The temperature must be a
room temperature before starting the system.

h) select “OPTIONS”, “SETUP SCALES” and Click to TARA ADJUSTMENT to calibrate the
Tara

i) Start the measurement by selecting “Start”, Check data collection and controller.
Click “OK” to start the measurement

j) Monitor the run using the real time graphic and current values windows.

k) Once the run is completed monitor the current values and do not lift the furnace and
o
protection tube until the temperature is less than 100 C.

B) Sample curve

1) Switch the balance to ON

2) Open the furnace “plug-in” on the top.

 Carefully remove the sample crucible.

• Clean the crucible or replace it if the old sample can not be cleaned from the
crucible.

• Inspect the Al2O3 reference material. If it is contaminated replace with new

Al2O3.

• Place equal amounts of Al2O3 in the reference and sample crucibles.

 • The normal amount is 1/3 full (max. 150 mg for sample and reference).

• Close the “plug-in” on the furnace top.

3) Start the software STA data collection software using the desktop icon

4) Select “DATA ACQUISITION”, “TYPE”, “sample TG+DTA”

5) Select “DATA ACQUISITION”, “SETTINGS…”

Enter the data collection information Text fields:

• Operator, Atmosphere,

• Laboratory,

• Flow Rate,

• Sample and Reference name,

• Comments

TG Sample File names: *.GPR extension will be automatically inserted

DTA Sample File name: *.TPR extension will be automatically inserted.

Enter the sample weight

The data acquisition termination is determined by the Duration and End Temp. value. Once
either value is reached the data collection will be terminated. Always select a time or
temperature higher than the final data point needed. Click “OK” to complete settings

6) Select “CONTROLLER”, “TEMPERATURE PROFILE…”

7) Enter the desired heating rate to the maximum temperature.

8) Select “CONTROLLER”, “CURRENT VALUES”.

9) Check the current furnace and sample temperature. The temperature must be a
room temperature before starting the system.

10) select “OPTIONS”, “SETUP SCALES” and Click to TARA ADJUSTMENT to calibrate
the Tara

11) Start the measurement by selecting “Start”, Check data collection and controller.
Click “OK” to start the measurement
 12) Monitor the run using the real time graphic and current values windows.

13) Once the run is completed monitor the current values and do not lift the furnace
o
and protection tube until the temperature is less than 100 C.

TGA is commonly employed in research and testing to determine characteristics of

materials such as polymers, to determine degradation temperatures, absorbed moisture content of
materials, the level of inorganic and organic components in materials, decomposition points of
explosives,melting,oxidation,evaporation and solvent residues. It is also often used to estimate
the corrosion kinetics in high temperature oxidation.

Example: TGA is a useful technique for assessing the effectiveness of oven drying solution
polymerized polymer samples. The volatilization of residual solvent is typically associated with
the initial weight loss process in a TGA heating run. In some cases, absorbed moisture may be
liberated over this same temperature range, though. After the initial solvent (or moisture) weight
loss process, TGA profiles will typically plateau to some constant weight level until the polymer
degradation temperature range is reached. The weight fraction of residual solvent (or moisture)
and the onset and maximum rate weight loss degradation temperatures are readily determined by
TGA.

Applications: TGA measures the weight change in materials as a function of time and
temperature. The measurements provide basic information about the thermal stability of a
chemical and its composition. TGA is one of the most commonly requested thermal techniques
and it is used to characterize both inorganic and organic materials, including polymers. The
measurement is typically carried out on milligram size samples with a heat rate of 10°C/min
from 20° to 1000°C in a nitrogen atmosphere.

Thermo-balance measurement of Calcium-oxalate

Calcium-oxalate: CaC2O4+1H2O

1. Stage: Dehydration: CaC2O4 + 1H2O CaC2O4 + H2O

Mass change: -12.3%

2. Stage: Building carboante: CaC2O4 CaCO3 + CO

Mass change: -19.2% (-31.5% total)

3. Stage: Decarbonation: CaCO3 CaO + CO2

Mass change: -30.1% (-61.6% total)

 QUICK Start Manual For Thermobalance PT 1000

Manuals for operation with sample or zero file

sample measurement 1000 °C

zero measurement 1000 °C

Measurement with sample (1000 °C)

- switch on Computer and Balance

- open top cover

- remove used crucible and clean it toughly

- insert new sample and weigh before

- place crucible onto measuring system (reference crucible empty)

- close top cover

- start software STA MEASUREMENT

- program CONTROLLER, TEMPERATURE PROFILE

- check CONTROLLER, CURRENT VALUE for temperature of sample and furnace

should be room temperature

- select DATA ACQUISITION, TYPE, SAMPLE TG+DTA

- program DATA ACQUISITION, SETTINGS

- sample file name, zero file name, weight of sample, duration,

end temperature, and ranges for TG and DTA , switch filter to √

- select OPTIONS, SETUP SCALES to find the Tara of the balance

- press AUTOMATIC ZERO ADJUSTMENT

- be sure SLIDER is OFF

- start measurement with START

(it is useful to start the measuring without the controller to see if the TG and the DTA

signal has no drift anymore. if it is ok stop measurement and start the whole experiment)

- monitor measurement with CONTROLLER CURRENT VALUES or

real time graphic

- after run is finished switch SLIDER in the menu OPTIONS to ON √ for faster cooling
 Measurement zero file (1000 °C)

- switch on Computer and Balance

- open top cover

- remove used crucible and clean it toughly

- place two empty clean crucibles onto measuring system

- close top cover

- start software STA MEASUREMENT

- program CONTROLLER, TEMPERATURE PROFILE

- One heating rate to the maximum, same gas conditions, and heating rate like in the
sample run

- check CONTROLLER, CURRENT VALUE for temperature of sample and furnace

should be room temperature

- select DATA ACQUISITION, TYPE, ZERO TG+DTA

- program DATA ACQUISITION, SETTINGS

- zero file name (should follow DOS conventions max. 8 characters or numbers only),
duration, end temperature, and ranges for TG 25mg and DTA 250uV, switch filter to √

- select OPTIONS, SETUP SCALES to find the Tara of the balance

- press AUTOMATIC ZERO ADJUSTMENT

- be sure SLIDER is OFF

- start measurement with START

(it is useful to start the measuring without the controller to see if the TG and the DTA

signal has no drift anymore. if it is ok stop measurement and start the whole experiment)
- monitor measurement with CONTROLLER CURRENT VALUES or

real time graphic

- after run is finished switch SLIDER in the menu OPTIONS to ON √ for faster cooling