Max Wellington

ID# UD3587SCH8551

Course:
INSTRUMENTAL METHODS : CHROMATOGRAPHY

Topic:
GAS CHROMATOGRAPHY AND ITS USE IN THE DETERMINATION OF OXALATES IN BAYER PROCESS
LIQUORS

ATLANTIC INTERNATIONAL UNIVERSITY

INTRODUCTION

 Organic carbon enters the Bayer process liquors from bauxite in the form of
humic substances (Rao and Goyal, 2006)
 5-10% of organic carbon is converted to Sodium Oxalate (Lever, 1983;
Grocott, 1988)
 The recycling of Bayer liquor will result in oxalate build up and ultimate
preciptation as fine needles in the cooler parts of the circuit (Sipos, 2001).
 Sodium oxalate has been shown to be harmful to alumina productivity and
size (Calalo and Tran, 1993; Brown and Cole, 1980) and so its control and
removal is critical to Bayer process productivity (The and Bush, 1987).
 Effective Oxalate control requires its accurate determination in process liquor
streams. Chromatography can be used to facilitate the isolation and
determination of oxalates from the milieu of structurally similar impurities as
found in Bayer liquor.
 This Presentation will look at the use of Gas Chromatography and its use in
the analysis of oxalate in Bayer liquor streams.
INTRODUCTION TO GAS CHROMATOGRAPHY

 Gas chromatography is a process by which a mixture is

separated into its constituents by a gas phase moving
over a stationary phase

 Mobile Phase: gas

 Stationary Phase : liquid (or solid)

 Advantages of Gas Chromatography

• High Resolution Separations

- Analysis of complex mixtures

• Greater sensitivity

• Better Peak Shape

-Greater Efficiency
-Greater Inertness
• More accurate Qualitative Analysis
- Analysis of Closely Related Substances
• More accurate Quantitative Analysis

• Easy to maintain and durable

Schematic of a Gas Chromatograph
 Overview

1. The sample solution is injected into the heated (250 oC) injection port where
it is rapidly volatilized

2. The volatilized sample is then swept via the carrier gas into the heated
column where volatile compounds separate and are eluted separately

3. The eluted compounds are then detected in a heated detector to give an

electrical signal which is amplified and recorded.

4. The output is a plot of detector response vs. time called a chromatogram

 Basic Principles of GC Separation

• Different compounds have different partition

coefficients, K

• Example: Compounds A and B

KA= CmA / CsA
KB= CmB / CsB

• CmA = conc. of A in mobile phase

• CsA = conc. of A in stationary phase

 Basic Principles of GC Separation

•If KA > KB then compound A spends more time on

average than compound B in the mobile phase

•Compound A migrates faster and separation occurs, and

A is eluted first

• The Partition coefficient, K depends on the volatility

(and bp) of the compounds being separated
 Elution from a GC Column

1. Compounds are eluted in order of volatility, ie the most

volatile (generally lowest boiling) off column first

2 . Compounds must be volatile to pass through the column

If not, they must be chemically modified to do so

Example:Liquor samples are converted to methyl esters in

order to make them volatile
 Separation Efficiency (Resolution)

The resolution (Rs) between two peaks in a chromatogram is given by:

where Z is the separation between peaks A and B; and Wa and Wb are the widths at the base of peaks A and B, respectively.

Acceptable resolution is on the order of Rs = 1.0, and baseline resolution between two peaks (as shown in the figure) requires an Rs > 1.5.
 GC Components

The major components of a GC system are:

• Gas supply

• Injection System

• Column

• Detector
• Oven
 Gas Supply

• Inert gases are commonly used as the Mobile Phase for GC work

• The most commonly used gases are Helium, Argon, Hydrogen

and
Nitrogen
• Some GC units use a detector gas depending on the application and
the type of detector.

• Example: Hydrogen gas is commonly used with a Flame Ionization

Detector (FID)
 Injection System

• The injection port consists of a rubber septum through which a syringe

needle is inserted to inject the sample.

• The injection port is maintained at a higher temperature than the boiling

point of the least volatile component in the sample mixture

• There are two types of injectors:

1. Normal Packed Column Injector
2. Split/Splitless capillary Injector

• In the packed column injector, ALL the vapourized sample enters onto
the column
• In the split/splitless injector the amount of vapourized sample that enters
onto the capillary column can be controlled
 Injectors

Schematic of packed GC column injector Schematic of split/splitless GC column injector

 GC Columns

• Gas chromatography columns are of two designs:

1. Packed column
2. Capillary column
• Packed columns are typically a glass or stainless steel coil(typically 1-5m
total length and 5mm inner diameter) that is filled with the stationary phase,
or a packing coated with the stationary phase

• Capillary columns are a thin fused-silica (purified silicate glass) capillary

(typically 10-100m in length and 250 micron inner diameter) that has the
stationary phase coated on the inner surface.

• Capillary columns provide much higher separation efficiency than packed

columns but are more easily overloaded by too much sample
 GC Columns

Picture of a packed GC column Picture of a capillary GC column

 Stationary Phases

• The most common stationary phases in gas chromatography columns are

polysiloxanes, which contain various substituent groups to change the
polarity of the phase.

• The nonpolar end of the spectrum is polydimethyl siloxane, which can

be made more polar by increasing the percentage of phenyl groups on
the polymer.
• For very polar analytes, polyethylene glycol (also known as carbowax)
is commonly used as the stationary phase
• After the polymer coats the column wall or packing material, it is often
cross-linked to increase the thermal stability of the stationary phase and
prevent it from gradually bleeding out of the column.
 Detectors

• After the components of a mixture are separated using gas chromatography,

they must be separated as they exit the GC column.The requirements of a
GC detector depends on the separation application.

• Example : One analysis might require a detector that is selective for

chlorine-containing molecules, another analysis might require a detector
that is non-destructive so that the analyte can be recovered for further
analysis
 Specific GC Detectors

• Flame Ionization Detector (FID)

The FID consists of a hydrogen / air flame

and a collector plate.Effluent from the GC
column passes through the flame which
breaks down organic molecules to produce
ions.The ions are collected on a biased
electrode and produces an electrical signal.
The FID is extremely sensitive and covers
many applications,and it’s only disadvantage
is that it destroys the sample.
 Specific GC Detectors

• Atomic Emission Detector (AED)

- Simultaneously determines the atomic emission of many elements in analyte that elutes from
GC capillary column.

• Chemiluminescence Detector (CD)

-Uses quantitative measurements of optical emission from excited chemical species to
determine analyte concentration (energized molecules)

• Electron Capture Detector (ECD)

-Uses a radioactive beta emitter (electrons) to ionize some of the carrier gas and produces a
current between a biased pair of electrodes.Has application for organic functional groups such
as halogens,phosphorus and nitrogen compounds.
• Flame Photometric Detector (FPD)
-Used to detect phosphorus and nitrogen containing compounds.Uses the chemilumiescent
reactions of these compounds in a hydrogen / air flame.
 Specific GC Detectors

• Mass Spectrometer (MS)

-Uses the difference in mass-to-charge ratio (m/e) of ionized atoms or molecules to separate them
from each other.
• Photo Ionization Detector (PID)
-Uses ultraviolet light as a means of ionizing an analyte exiting from a GC column

• Thermal Conductivity Detector (TCD)

-Consists of an electrically-heated wire or thermistor.Changes in thermal conductivity such as
when organic molecules displace some of the carrier gas, cause a temperature rise which is sensed
as a change in resistance.Change in resistance is proportional to the amount of analyte. The
TCD is not as sensitive as the other detectors but it is non-specific and non-destructive.
• Nitrogen-Phosphorus Detector (NPD)
-Similar in design to a FID but with selectivity for compounds containing nitrogen and
phosphorus.
GC Oven
 GC Oven

•The oven consist of a wire coil that radiates into the inner volume of the
oven.Heat from the resistive wire source is spread in an even manner,
throughout the oven volume using a fan attached to an electric motor. A
thermocouple inside the oven is part of regulating the oven temperature
via the amount of heat released by the heating element.
• The GC oven is used to keep the column at temperatures between 40 to
350oC

• Most liquids must be converted to vapour state and maintained as a

vapour
throughout the GC separation
• GC ovens are temperature-programmed to allow separation of analytes
spanning a range of vapour pressures in a single analysis
 Quantification in GC

Internal Standard Method

• A known amount of reference substance is added to the sample before
injection onto the column.
Why use an internal standard?
• It eliminates any variations in those factors which influence the sensitivity
and response of the detector.

Characteristics of an Effective Internal Standard

• The internal standard must be volatile
• The internal standard must produce completely resolved (separated)
peaks in the chromatogram, and be eluted close to the analytes of interest.
 Quantification in GC

•The peak height or peak area for the internal standard peak
in the chromatogram should be similar to those of
the components to be measured.

• The internal standard should be chemically similar to the sample components

of interest.

• The compound to be used as the internal standard must not be naturally

present in the original sample.
 Oxalate Analysis by GC

• Oxalate standards are prepared from pure Sodium Oxalate,dried at 110oC

for five hours.
• Both standard and samples are diluted with de-ionized water
• An internal standard and derivatizing reagent components are added to
both standards and samples.
• Standard and samples are then digested at 65oC for 30 minutes in a water
bath fitted with a rotating carousel.
• The organic layer of each standard and sample is extracted and placed in
2ml vial which are sealed with a rubber cap.
• Both standards and samples are analyzed using GC.
• Calibrations and results are processed using the instrument software.
 Reagents used and Reason(s)

Monochloroacetic acid
-Used as an internal standard.Very similar in structure and has a different
retention time to the peaks of interest.Also,it is not present in the samples

Methanol
-The compounds are converted to the methyl esters using the methanol as
these have relatively simple structure, low boiling points, and can be easily
analyzed using FID detectors.
Sulphuric Acid
-Strong, pure acid is used to increase the ionic strength of the solution and increase
the partition coefficient between the aqueous and organic layers.
Chloroform
-The organic layer to which the methyl esters are extracted.Has the advantage of
being a low boiling point solvent, which allows the sample to be vapourized and
analyzed by GC FID.Also, it is not miscible with water.
Bayer Liquor Chromatogram from GC unit
(Oxalate elutes at 3.25 minutes)
 Discussion and Conclusion

 Gas chromatography presents a simple and relatively rapid method

for oxalate determination in Bayer liquor streams. The sample oxalate
concentration is determined by comparing with peak area of internal
standard.
 Gas chromatography is less costly in terms of maintenance when
compared to ion chromatography as ion chromatogram requires the
regular replacement of Guard Columns, Analytical Columns and
Suppresors which are quite costly.
 In Bayer plants where Sulfate and Chloride levels are a concern then
ion chromatography may be the method of choice as it can analyze
each sample for a number of anions e.g Sulfate, Chloride, Oxalate,
Fluoride, Nitrate and Phosphate (see Appendix 1) whereas the Gas
Chromatogram can only be used for specified organic analyses of
which only oxalate is of major concern to Bayer process operations.
Reccomendations

 Gas Chromatography be used for the analysis of oxalates in Bayer

process liquor streams in instances where anions such as Sulfate and
Chlorides are not a concern.
 In cases where anions such as Sulfates and Chlorides are a concern
then it is reccomended that ion chromatography be used.
References

 Barnett N W, Bowser T A and Russel R A (1995) Determination of oxalate in alumina process liquors by ion
chromatography. Analytical Proceedings and Communications, Vol 32, p57-59.
 Brown N and Cole T J (1980) The behaviour of sodium oxalate in a Bayer alumina plant. Light Metals, 105-117.
 Calalo R and Tran T (1993) Effects of sodium oxalate on the precipitation of alumina trihydrate from synthetic
sodium aluminate liquors. Light Metals, 125-133.
 Grocott S C (1988) Bayer liquor impurities:measurement of organic carbon, oxalate and carbonate extraction from
bauxite digestion. Light Metals, 833-841.
 Harris Daniel (1996) Exploring chemical analysis. W.H. Freeman and Company, New York.
 Lever G (1978) Identification of organics in Bayer liquor (1978) Light Metals, 71-83.
 Rao K V and Goyal R N (2006) Organic carbon in indian bauxites and its control in alumina plants. Light Metals,
71-74.
 Sipos G (2001) The mechnism and action of sodium oxalate seed stabilizer molecules under Bayer conditions. PhD
Thesis, School of Applied Chemistry, Curtin University of Technology, Australia.
 Skoog D A, Holler J F and Nieman T (1998) Principles of instrumental analysis. Harcourt and Saunders College
Publishing, Chicago.
 The P J and Bush J F (1987) Solubility of sodium oxalate in Bayer liquor and a method of control. Light Metals, 5-
10.
 Appendix
Ion Chromatogram of an Anion Standard Solution (Dionex, 1998)
(Oxalate elutes after 8 Minutes)
Acknowledgment

 Acknowledgment is extended to Mr Glenroy

Lawrence, Chemist of Jamalco for supplying
some of the data used in this presentation.