TITLE: Determining the Thermal Behaviour and Composition of Calcium Oxalate

Monohydrate.

OBJECTIVES:

1. To explain the principle of Thermogravimetry.

2. To explain the TG curve and identify the significant information from the curve.

3. To determine the percent of element exist in the compound based on the percent of

weight loss / gain.

INTRODUCTION:

Thermogravimetry analysis (TGA) which involve continuously measuring the changes of

mass of a sample as a function of it temperature.When a material is heated its structural and

chemical composition can undergo changes such as fusion, melting, crystallization,oxidation,

decomposition, transition, expansion, and sintering. Thermal analysis such changes can be

monitored in every atmosphere of interest. In TGA the exact mass of sample is determine while

it undergoes a temperature treatment. It is possible to keep the sample at a constant temperature

or a linear temperature gradient can be applied. Alternatively, the sample can be heated until a

constant mass is obtained. TGA was used in application of sample purity, decomposition,

dehydration, and oxidation.

A thermal analysis system contains a graphite resistor furnace that can heat a sample

from room temperature to 1000 ˚C. The atmosphere in the system can be either inert such as

vacuum, nitrogen, helium, and argon to protect the sample from oxidation or active such as air,

oxygen, and hydrogen to react with the sample. To determine weight changes of the sample
during heating a balanced was used. The sample pan which is used to place the sample was made

up from platinum or ceramic alumina.

From thermogravimetry curve we can get information the decomposition of the

sample and the changes of mass of sample.

PROCEDURE:

A. Determining the thermal composition of Calcium Oxalate Monohydrate (CaC2O4.H2O)

0.1000 g of Calcium Oxalate Monohydrate was weighed precisely.

The sample was put into the crucible and then into the furnace.

The temperature of the furnace was programmed between 50⁰C to 1100⁰C with

increment of 25⁰C per minute.

The thermogram obtained was analyzed based on the example from text book.

B. Determining the composition of a mixture (CaC2O4.H2O and Na2C2O4)

The mixture sample was weighed precisely 0.1000 g.

The test carried out in (A) was repeated.

The percentage of CaO in the mixture sample was determined.

RESULT:

A. Determining the thermal composition of Calcium Oxalate Monohydrate (CaC2O4.H2O)

Stage x1 (⁰C) x2 (⁰C) y1 (%) y2 (%) ∆y (%)

1 101.225 181.642 99.8574 87.9110 11.9464
2 377.953 486.752 87.4242 68.8883 18.5359
3 597.917 770.576 68.0931 38.8318 29.2613

B. Determining the composition of a mixture (CaC2O4.H2O and Na2C2O4)

Stage x1 (⁰C) x2 (⁰C) y1 (%) y2 (%) ∆y (%)

1 97.725 153.213 99.8545 93.5472 6.3073
2 389.637 471.663 92.9174 83.2135 9.7039
3 474.075 556.100 83.0803 74.7011 8.3792
4 597.113 749.100 74.0759 57.9326 16.1433

CALCULATION:

A. Determining the thermal composition of Calcium Oxalate Monohydrate (CaC2O4.H2O)

Mr of CaC2O4.H2O = 40.078 + (12.0107 × 2) + (15.9994 × 4) + (1.00794 × 2) + 15.9994

= 146.1123 g mol-1

(i) Stage 1

a) Equation of the reaction:

CaC2O4.H2O ∆ CaC2O4 + H2O

b) Mass of H2O released

∆y
= × mass of CaC2O4.H2O
100

11.9464
= × 17.338 mg = 2.0713 mg
100
 c) Mass of CaC2O4 = Mass of sample – Mass of H2O released

= (17.338 – 2.0173) mg = 15.2667 mg

d) Number of moles of H2O released

mass 0.0020173 g
n= = = 1.1198×10-4 mol
Mr 18.0153 g /mol

e) Number of moles of CaC2O4

mass 0.0152667 g
n= = = 1.1918×10-4 mol
Mr 128.09702 g/mol

f) % of H2O released (theoretical)

Mr of H 2 O 18.0153
= × 100% = × 100% = 12.3298%
Mr of Ca C 2 O 4 . H 2 O 146.1123

g) % of H2O released (experimental)

Mass of H 2 O 2.0173 mg
= × 100% = × 100% = 11.6351 %
Massof Ca C2 O4 . H 2 O 17.338 mg

h) % of error

¿
= ¿ Theoretical %−Experimental %∨ Theoretical % ¿ × 100% =

¿ 12.3298−11.6351∨ ¿ ¿
12.3298 × 100% = 5.6343 %

(ii) Stage 2

a) Equation of the reaction:

CaC2O4 ∆ CaCO3 + CO

b) Mass of CO released

∆y
= × mass of CaC2O4.H2O
100

18.5359
= × 15.2667 mg = 2.8298 mg
100
 c) Mass of CaCO3 = Mass of sample – Mass of CO released

= (15.2667 – 2.8298) mg = 12.4369 mg

d) Number of moles of CO released

mass 0.00 28298 g

n= = = 1.0103×10-4 mol
Mr 28.0101 g/mol

e) Number of moles of CaCO3

mass 0.0124369 g
n= = = 1.2426 ×10-4 mol
Mr 100.0869 g /mol

f) % of CO released (theoretical)

Mr of CO 28.0101
= × 100% = × 100% = 21.8663 %
Mr of Ca C 2 O 4 128.09702

g) % of CO released (experimental)

Mass of CO 2.8298 mg
= × 100% = × 100% = 18.5358 %
Massof Ca C2 O4 15.2667 mg

h) % of error

¿
= ¿ Theoretical %−Experimental %∨ Theoretical % ¿ × 100% =

¿ 21.8663−18.5358∨ ¿ ¿
21.8663 × 100% = 15.2312 %

(iii) Stage 3

a) Equation of the reaction:

CaCO3 ∆ CaO + CO2

b) Mass of CO2 released

∆y
= × mass of CaCO3
100

29.2613
= × 12.4369 mg = 3.6392 mg
100
 c) Mass of CaO = Mass of sample – Mass of CO2 released

= (12.4369 – 3.6392) mg = 8.7977 mg

d) Number of moles of CO2 released

mass 0.00 36392 g

n= = = 8.2691 ×10-5 mol
Mr 44.0095 g/mol

e) Number of moles of CaO

mass 0.0 87977 g

n= = = 1.5688 ×10-3 mol
Mr 56.0774 g /mol

f) % of CO2 released (theoretical)

Mr of C O 2 44.0095
= × 100% = × 100% = 43.9713 %
Mr of CaC O 3 100.0869

g) % of CO2 released (experimental)

Mass of C O 2 3.6392mg
= × 100% = × 100% = 29.2613 %
Massof CaC O 3 12.4369mg

h) % of error

¿
= ¿ Theoretical %−Experimental %∨ Theoretical % ¿ × 100% =

¿ 43.9713−29.2613∨ ¿ ¿
43.9713 × 100% = 33.4356 %

i) % of CaO (theoretical)

Mr of CaO 56.0774
= × 100% = = × 100% = 56.0287 %
Mr of CaC O 3 100.0869

j) % of CaO (experimental)

Mass of CaO 8.7977 mg

= × 100% = = × 100% = 70.7387 %
Massof CaC O3 12.4369mg

B). Determining the composition of a mixture (CaC2O4.H2O and Na2C2O4)

(i) Stage 1

a) Equation of the reaction:

CaC2O4.H2O + Na2C2O4 ∆ CaC2O4 + Na2C2O4 + H2O

b) Mass of H2O released

∆y
= × mass of (CaC2O4.H2O + Na2C2O4)
100

6.3073
= × 17.151 mg = 1.0818 mg
100

c) Mass of CaC2O4 + Na2C2O4 = Mass of sample – Mass of H2O released

= (17.151 – 1.0818) mg = 16.0692 mg

d) Number of moles of H2O released

mass 0.0010818 g
n= = = 6.0049 ×10-5 mol
Mr 18.0153 g /mol

e) Number of moles of CaC2O4 + Na2C2O4

mass 0.0160692 g
n= = = 6.1310 ×10-5 mol
Mr 262.0955 g /mol

f) % of H2O released (theoretical)

Mr of H 2 O 18.0153
= × 100% = × 100% = 6.8736 %
Mr of Ca C 2 O 4 . H 2 O+ Na 2 C 2 O 4 262.0955

g) % of H2O released (experimental)

Mass of H 2 O 1.0818 mg
= × 100% = × 100% = 6.3075 %
Massof Ca C2 O4 . H 2 O+ Na2 C 2 O4 17.151mg

h) % of error

¿
= ¿ Theoretical %−Experimental %∨ Theoretical % ¿ × 100% =

¿ 6.8736−6.3075∨ ¿ ¿
6.8736 × 100% = 8.2359 %
DISCUSSION:

TGA measures the amount of weight change of a material, either as a function of

increasing temperature, or isothermally as a function of time, in an atmosphere of nitrogen,

helium, air, other gas, or in vacuum. Thermal gravimetric analysis can be interfaced with a mass

spectrometer RGA to identify and measure the vapors generated, though there is greater

sensitivity in two separate measurements. Inorganic materials, metals, polymers and plastics,

ceramics, glasses, and composite materials can be analyzed. The temperature range from 25°C to

900°C routinely. The maximum temperature is 1000°C.

Sample weight can range from 1 mg to 150 mg. Sample weights of more than 25 mg are

preferred, but excellent results are sometimes obtainable on 1 mg of material. The weight change

sensitivity of 0.01 mg. Samples can be analyzed in the form of powder or small pieces so the

interior sample temperature remains close to the measured gas temperature.

Using themogravimetry method, there are some sample that cannot be analyzed by using

this method, which are gas and explosive material.

From the graph, initial there is no changes. Then the curve going down show that the mass of

sample was reduced. The higher the temperature, the sample decomposition increase and the

mass of sample reduced.

The applications of thermogravimetric analysis are to determine temperature and weight

change of decomposition reactions, which often allows quantitative composition analysis. It may

be used to determine water content. TGA allows analysis of reactions with air, oxygen, or other

reactive gases. TGA can be used to measure evaporation rates, such as to measure the volatile
emissions of liquid mixtures. It allows determination of Curie temperatures of magnetic

transitions by measuring the temperature at which the force exerted by a nearby magnet

disappears on heating or reappears on cooling. TGA also helps to identify plastics and organic

materials by measuring the temperature of bond scissions in inert atmospheres or of oxidation in

air or oxygen. It is used to measure the weight of fiberglass and inorganic fill materials in

plastics, laminates, paints, primers, and composite materials by burning off the polymer resin.

The fill material can then be identified by XPS and/or microscopy. The fill material may be

carbon black, TiO2, CaCO3, MgCO3, Al2O3, Al(OH)3, Mg(OH)2, talc, Kaolin clay, or silica, for

instance

PRECAUTIONARY STEPS:

1. Never used the sample which flammable or explosive materials. These samples can cause

explosion due to the thermal effect of the apparatus.

2. The mass of the sample must be accurately measured to make sure no error in the

analysis.

3. Use the specified tools in order to transfer the sample into the thermobalance.

CONCLUSION:

1. TGA is the second most commonly used thermal technique. It measures weight changes

in a material as a function of temperature (or time) under a controlled atmosphere. Its

principal uses include measurement of a material's thermal stability and composition.

TGA instruments are routinely used in all phases of research, quality control and

production operations.
 2. The significant information can be explained by the TG curve are the percent of

decomposition of the sample, the temperature at which it decomposed.

3. The percentage of element exist in the compound can be determined based on the percent

of weight loss or gain.

REFERENCES:

1. Gary D.Christian: Analytical Chemistry Sixth Edition, John Wiley and Sons, New York:

p. (604-630)

2. http://pediaview.com/openpedia/Thermal_analysis

3. http://www.patents.com/furnace-differential-thermal-analysis-4149401.html

QUESTIONS:

1. In thermal analysis, the effect of furnace atmosphere is important beside in controlling

the temperature of the sample, the measurement may be carried out in air or under an

inert gas. Reducing or reactive atmosphere have also been used and measurement are

even carried out with the sample surround by water or other liquid. Before burning the

sample, make sure the neutral gas in the furnace has been released to stabilized the

sample, make sure the decomposed material has been released and keep the balance in

good condition.

2. The thermocouple that made of combination of two metals that have different melting

point which is the lowest and the highest melting point. For example, antimony and

bismuth. When a temperature difference exists between two points, a potential difference
 is developed can be measure. The thermocouple seldom immersed directly into the

sample to accurately measure the temperature.

3. There are other methods of thermal analysis beside thermogravimetry analysis are

Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC).

Differential Thermal Analysis (DTA) the property is temperature different. The

applications are for reaction, dehydration, decomposition and phase changes. While

Differential Scanning Calorimetry (DSC), the property for energy difference, the

applications are for heat capacity, phase changes, reaction, and calorimetry.