Gamal A.

Hamid 1
 • Introduction • Analysis

• Theory • Applications

• Hardware ▫ Environmental
▫ Oil and Gas
Injector
▫ Food
Column
▫ Pharmaceutical
Detector
▫ Forensic / Clinical
Oven
Carrier gas
• Sample preparation

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Gamal A. Hamid 3
 Declaration

Experience has shown that maximum value can be derived from a scientific instrument
if there is

one person who has a major responsibility for the instrument.

We recommend that you designate a key operator to manage the operation and
maintenance of the TRACE system. We also recommend that the key operator
receive training .
Thermo Finnigan Italy

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 Gas Chromatography

Gas Chromatography

• A separation technique in which the mobile

phase is a gas. Gas chromatography is always
carried out in a column.
• Separating mixtures of gases or volatile
materials based primarily on their physical
properties.
• It gives both
1- Quantitative
2-Qualitative

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 Major Current GC Markets

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Gamal A. Hamid 7
 Theory

Chromatographic separation involves the use of

Components of mixture carried in the mobile phase are differentially attracted to the
stationary phase and thus Move through the stationary phase at different rates.

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 Generally

o Boiling points is The number one factor to consider in

separation of compounds on the GCs.

o Differences in polarity of the compounds is only

important if you are separating a mixture of

compounds which have widely different polarities.

o Column temperature, the polarity of the column, flow

rate, and length of a column are constant .

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Gamal A. Hamid 10
 Sample Preinjection

Liquid introduction by syringe

▫ Most commonly used technique
▫ Different syringe types manual and automatic

Other techniques and devices

▫ Sampling valve (gas or liquids)
▫ Head-space (liquids or solids)
▫ Purge and trap (water)
▫ Thermal desorption (solids)
▫ SPME (vapours, liquids or solids)
▫ Pyrolizer (solids)

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 Manual injection

Micro Syringes

Syringes are used to introduce a known volume of a liquid or gas samples.

Adaptor can be used to help control the volume injected

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 Syringe injection

1- Samples should be injected as a plug.

2- Rapid and consistent injection is necessary

in order to obtain Acceptable precision

Injection Volume

1- Liquids 0.1-10 ul is typical

2- Gases 0.5- 5 ml is typical

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 Hot Needle injection
1- Draw sample into syringe barrel.

2- Draw 2-3 ul air into barrel.

3- Inset needle into injection port and allow

to heat for a few seconds.

4- Rapidly inject sample and withdraw the needle.

5- This insure that all sample is injected and the hot needle

assists in solvent volatilization.

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 Normal injection

1- Rinse the syringe with your sample at least twice .

2- Draw up the suggested amount of sample into the syringe.

3- Pull up about 1-2 ul of air. This will give a signal showing the beginning of the elution.

4- Insert the needle through the injection port and septum in one movement.

5- Quickly push the plunger.

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 Automatic injection

Auto sampler

Sample loading
Sample capacity: 8/105 Vials
Max. vial capacity: 2 ml
Injections/vial: 0-99

Syringes
Standard sampling: 10µl
Micro volume sampling: 5µl

Injection parameters
Max volume: 5µl
Min. Volume : 0.1µl AS 3000
Increments: 0.1µl steps
Viscosity Delay: Yes/No

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 Auto sampler

Large sample vial capacity - Max 2 trays installed simultaneously

1, 2 and 2.5 ml vials (up to 300 vials)
Syringe size: - 5, 10, 100 and 250 µl.
Self recognized - syringes and trays
washing station: - 4 x 10ml or 2 x 100ml; multiple
solvent rinsing supported

Rapid Mode: Allows to perform cleaning operations

TriPlus Autosamplers
during GC run or cooling time.
Suitable for Ultra Fast GC requirements, eliminating dead times between
successive runs.

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 Other techniques

Manual Sampling valve (gas)

In quantitative gas chromatographic determination of a gas mixture,

the sample must be introduced in reproducible amounts .

This device, shown in Figure allows to introduce a precise amount

of gas sample into the chromatographic column with a simple rapid operation.

Principle
For manual gas sampling, a 6-port valve is used.

A wide range of sampling loops allows the injections

of different volumes of sample.
The switching from load sample to inject sample position (and vice-versa) is
performed by rotating the valve rotor knob manually.

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 Head Space

Head-space gas analysis

- Volatiles reach equilibrium at STP

- An aliquot of headspace is total in liquid and gas phase

- Conc. in gas proportional Conc. In liquid phase

With headspace matrix left behind

- Clean and gentle chromatography

representative of sample

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 Head-space applications

1- Determination of residual volatile solvents in pharmaceutical

2- Blood alcohol analysis – AN9140

3- Determination of volatile hydrocarbons in waste water

4- Determination of di-acetyl and dichetones in beers

5- Monomers in polymers determination

6- Determination of out-gassing solvents from packages

7- Flavor profiles in drinking beverages or foods (cheese)

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 Cold and trap

 allows the analysis of trace of compounds in large volumes

of gaseous samples.
 the column can be cooled down to -150 °C by the action of
the liquid nitrogen,
 so to trap (i.e. to reconcentrate) the volatile compounds
contained in the sample.
 When the trapping is completed, the tube is heated with a
fast temperature programming rate (°C/s), reaching
temperatures up to 400 °C, so to transfer
the trapped compounds into the analytical column.

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 GC Basic Components

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 Injector .1

The injection port Is a hollow, heated, glass-lined cylinder .

1- The injector is heated so that all

components in the sample will be vaporized.
2- If the temperature is too low, separation is poor and
broad spectral peaks should result or no peak develops at all.
3- If the injection temperature is too high, the
specimen may decompose or change its structure.
4- The temperature of the sample port is usually
about 50°C higher than the boiling point of the least volatile component
of the sample.

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 Injection techniques

Vaporizing.
The liquid sample is evaporated prior to be transferred to the
separation column
▫ Split Spliless: SSL (permanently hot)
▫ Programmed Temperature Vaporizer: PTV
▫ Direct: PKD, PPKD (permanently hot, low resolution columns)

Nonvaporizing.
The liquid sample evaporates into the separation column (or a
precolumn)
▫ Cold On Column: OC (permanently cool)

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 Injector types

1. Split/ Splitless Injector

2. On-Column Injector

3. High Oven Temperature On-Column Injector

4. Large Volume On-Column Injector

5. Packed Column Injector

6. Purged Packed Injector

7. Programmable Temperature Vaporizing Injector

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 1. Split/Splitless Injector
(vaporising injector)
• Split mode

1. The split vent is open, part of the sample go into the column.

2. When analyzing high concentration or neat samples.

3. Yields the sharpest peaks if the split gas is properly mixed.

4. Standard for capillary columns.

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 Splitless mode

1. The split vent is closed, most of the sample go into the column.

2. When analyzing low concentration or diluted samples.

3. Splitless times of ~ 1 minute are typical.

4. Standard for capillary columns.

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 2. On-Column Injector

Non- vaporising injectors

1. The sample is transferred as a liquid directly inside the column

under the oven temperature control. The sample evaporation takes

place inside the column.

2. Sample doesn’t come in contact with any “column-external” device

3. No vaporization step at a temperature above that of the column

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 • Primary cooling
▫ Permanently active fan
▫ Keep the injector head at room temperature independently from oven temperature

• Secondary cooling
▫ Temporary stream of compressed air
▫ Avoid evaporation from the needle even at oven T close or slightly higher than BP
▫ Reduces the length of the flooded zones
▫ Avoid liquid backflow reducing the vapor pressure at the plug front
▫ More eefficient and rapid cooling of the injector base after a temperature ramp

• Cooling Time The amount of time the secondary cooling stays on after the start the
injection.

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 3. High Oven Temperature On-Column Injector

1- The OCI is the same as the regular cold on column except that a cooling
jacket is installed in the GC oven around the head of the column.
2- This allows a cold on column injection with a high oven temp.

Temperature (°C).

1- The temp. checkbox checked for this option to be used.

2- This specifies cooling jacket temp. during injection.
3- Duration (min) the duration of the jacket cooling from the start of the run

4. Large Volume On-Column Injector

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 5. Packed Column Injector

1. Injection directly into metal or glass packed columns with

or without glass liner.
2. The temp. is usually selected to be 20 ºC above the
evaporation temp. for all sample.
3. Optimum temp. varies with the method and sample
requirements.

6. Purged Packed Injector

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 PTV Injector

7. Programmable Temperature Vaporizing

Injector

1. Can vary the temp. during injection in both split and Splitless.
2. Can eliminate many of the unwanted effects , such as distillation of the sample
within the needle and large vapor clouds inside injector chamber.
3. In Constant Temperature (CT) mode, the PTV functions like a split/splitless injector.
4. Sample volumes are lower than when using S/SL injector because of the smaller
PTV liner volume .
5. Can analyze relatively dirty samples that can not be analyzed using a traditional on-
column technique.

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 Head-space applications

1. Determination of residual volatile solvents in pharmaceutical

2. Blood alcohol analysis – AN9140

3. Determination of volatile hydrocarbons in waste water

4. Determination of di-acetyl and dichetones in beers

5. Monomers in polymers determination

6. Determination of out-gassing solvents from packages

7. Flavor profiles in drinking beverages or foods (cheese)

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 Good injector

1. Capable to quantitative accept a broad volatility range of sample components .

2. Low discrimination.
3. To handle dirty and clean matrices.
4. With dirty matrices reduces sample clean-up and preserves the column.
5. With clean matrices boosts sensitivity with LVI techniques .
6. Extremely inert.
7. Able to handle polar/active compounds.
8. Provide optimum band shape.

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 GC Basic Components

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 Column .2

The column

• is where the chromatographic separation of the sample occurs.

• Several types of columns are available for different chromatographic

applications:

• The heart of the system.

• It is coated with a stationary phase which greatly influences the

separation of the compounds.

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 Stationary phase

 Solid resin packed in a column , or

 Liquid supported by course paper or

 Inactive solid over which a mixture passes.

Each component of the mixture differs in the way it adheres to this phase
and therefore travels along it at a unique rate.

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 The Adsorbents

There are two types of packing employed in GC, the adsorbents and the supports, on which
the stationary phase is coated.
There are both inorganic and organic types of adsorbents.

•Alumina, in an activated form, is used to separate the permanent gases and hydrocarbons
up to about pentane.
•Silica gel It is used for the separation of the lower molecular weight gases and some of the
smaller hydrocarbons sulfur gases, hydrogen sulfide, sulfur dioxide and carbon disulfide.
•Synthetic zeolites used for the separation of hydrogen, oxygen, nitrogen, methane and
carbon monoxide and also rare gasses.

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 Liquid supported
Types of stationary phase

 POLYSILOXANES
• The most common stationary phases.
• They are available in the greatest variety and are the most stable, robust and
versatile.
• The most basic Polysiloxanes is the 100% methyl substituted
 POLYETHYLENE GLYCOLS
• They are less stable, less robust and have lower temperature limits than most
Polysiloxanes.
• must be liquids under GC temperature conditions.

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 Inactive solid supports

• There have been a number of materials used as supports for

packed GC columns including,

• Celite (a proprietary form of a diatomaceous earth), fire-

brick (calcined Celite), fire-brick coated with metallic silver

or gold, glass beads, Teflon chips and polymer beads.

• polystyrene beads

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 Column types

1- Conventional
1/8-1/4 OD 6-8 feet in length
Stainless steel or glass tube

2- Preparative
>1/4 OD
> 10 feet in length

2- Capillary
0.1- 0.5 ID
10 – 100 meters in length

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 Factors affecting column separations

 Volatility of compound: Low boiling (volatile) components will

travel faster through the column than will high boiling components

 Polarity of compounds: Polar compounds will move more slowly,

especially if the column is polar.

 Column temperature: Raising the column temperature speeds up

All the compounds in a mixture.
Columns have lower and upper temperature limits.

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  Column packing polarity: Usually, all compounds will move slower on

polar columns, but polar compounds will show a larger effect.

 Flow rate of the gas through the column: Speeding up the carrier gas flow
increases the speed with which all compounds move through the column.

 Length of the column: The longer the column, the longer it will take all
compounds to elute. Longer columns are employed to obtain better separation.

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 Generally

 Boiling points is The number one factor to consider in separation of

compounds on the GCs.

 Differences in polarity of the compounds is only important if you are

separating a mixture of compounds which have widely different polarities.

 Column temperature, the polarity of the column, flow rate, and

length of a column are constant .

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 Loss of Separation or Resolution

1- Contaminated column.

2- Damaged stationary phase.

3- Different column temperature, carrier flow rate or column.

4- Large changes in the sample concentration.

5- Improper injector operation.

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 Column Damage

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 Column Bleed

It is the continuous elution of the compounds produced

from normal degradation of the stationary phase.

is the background generated by all columns

Column bleed increases at higher temperatures.

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 Rapid Column Deterioration

1. Exposure of the column to air (oxygen) .

2. Exceeding the upper temperature limit of the column

for prolonged periods.

3. Chemical damage.

4. Contamination of the column with high molecular weight materials.

5. Column breakage.

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 GC Basic Components

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 Oven .3

1. The use of a temperature programme for the column oven

influences the separation process significantly and is used for

optimization of time and peak separation.

2. The oven must not be opened when the oven temperature is

above room temperature.

3. Never turn off the nitrogen flow unless the column and oven are

at room temperature.

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 The Oven capabilities

• Temperature range 5 °C above ambient to 350 °C

• Temperature programming - up to six ramps

• Maximum run time - 999.99 minutes

• Temperature ramp rates - 0 to 120°C/min

• The oven accommodates one inlet, one detector,

and one column.

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 Multiple-ramp temperature programs

 A multiple-ramp temperature program changes the oven temperature

from an initial value to a final temperature, but with various rates, times,
and temperatures in between.
 Multiple ramps can be programmed for temperature decreases as well as

Increases.

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 GC Basic Components

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 Detector .4

The part of a gas chromatograph which signals the

change in composition of the mixture passing through it.

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 Detector types

1. Electron Capture Detector.

2. Flame ionization Detector.

3. Nitrogen Phosphors Detector.

4. Thermal Conductivity Detector.

5. Flame Photometric Detector.

6. Photo ionization Detector.

7. Electrolytic Conductivity Detector.

8. Mass Spectrometric Detector.

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 Electron Capture Detector .1
)ECD(

 Mechanism:

Electrons are supplied from a 63Ni foil lining the detector cell. A current is generated in
the cell. Electronegative compounds capture electrons resulting in a reduction in the
current. The amount of current loss is indirectly measured and a signal is generated.

Selectivity: Halogens, nitrates and conjugated carbonyls

Sensitivity: 0.1-10 pg (halogenated compounds);
1-100 pg (nitrates); 0.1-1 ng (carbonyls)
Linear range: 1000-10000
Gases: Nitrogen or argon/methane
Temperature: 300-400°C

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 Flame ionization Detector .2
)FID(

 Mechanism:

Compounds are burned in a hydrogen-air flame. Carbon containing compounds

produce ions that are attracted to the collector. The No.
of ions hitting the collector is measured and a signal is generated.

Selectivity: Compounds with C-H bonds. A poor

response for some non-hydrogen containing
organics (e.g., hexachlorobenzene).
Sensitivity: 0.1-10 ng
Linear range: 105-107
Gases: Combustion hydrogen and air; Makeup He or N2
Temperature: 250-300°C,and 400-450°C for high temp.

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 Nitrogen Phosphors Detector .3
)NPD(
 Mechanism:

Compounds are burned in a plasma surrounding a rubidium bead supplied with

hydrogen and air. Nitrogen and phosphorous containing compounds produce ions
that are attracted to the collector. The number of ions hitting the collector is
measured and a signal is generated.

Selectivity: Nitrogen and phosphorous

Containing compounds
Sensitivity: 1-10 pg
Linear range: 104-10-6
Gases: Combustion - hydrogen and air;
Makeup - Helium
Temperature: 250-300°C

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 Thermal Conductivity Detector.4
)TCD(

 Mechanism:

A detector cell contains a heated filament with an applied current. As carrier

gas containing solutes passes through the cell, a change in the filament
current occurs. The current change is compared against the current in a
reference cell. The difference is measured and a signal is generated.

Selectivity: All compounds except for the carrier gas

Sensitivity: 5-20 ng
Linear range: 105-106
Gases: Makeup - same as the carrier gas
Temperature: 150-250°C

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 Flame Photometric Detector .5
)FPD(
 Mechanism:

Compounds are burned in a hydrogen-air flame. Sulfur and phosphorous

containing compounds produce light emitting species (sulfur at 394 nm
and phosphorous at 526 nm). A monochromatic filter allows only one of
the wavelengths to pass. A photomultiplier tube is used to measure the
amount of light and a signal is generated. A different filter is required
for each detection mode.

Selectivity: Sulfur or phosphorous containing compounds.

Only one at a time.
Sensitivity: 10-100 pg (sulfur); 1-10 pg (phosphorous)
Linear range: Non-linear (sulfur); 103-105 (phosphorous)
Gases: Combustion - hydrogen and air; Makeup - nitrogen
Temperature: 250-300°C

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 Photo ionization Detector .6
)PID(

 Mechanism:

Compounds eluting into a cell are bombarded with high energy photons emitted
from a lamp. Compounds with ionization potentials below the photon energy are
ionized. The resulting ions are attracted to an electrode, measured, and a signal is
generated.

Selectivity: Depends on lamp energy. Usually used for

aromatics and olefins (10 eV lamp).

Sensitivity: 25-50 pg (aromatics); 50-200 pg (olefins)

Linear range: 105-106
Gases: Makeup - same as the carrier gas
Temperature: 200°C

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 Electrolytic Conductivity Detector .7
)ELCD(
 Mechanism:

Compounds are mixed with a reaction gas and passed through a high temperature
reaction tube. Specific reaction products are created which mix with a solvent and
pass through an electrolytic conductivity cell. The change in the electrolytic
conductivity of the solvent is measured and a signal is generated. Reaction tube
temperature and solvent determine which types of compounds are detected.

Selectivity: Halogens, sulfur or nitrogen containing compounds.

Only one at a time.
Sensitivity: 5-10 pg (halogens); 10-20 pg (S); 10-20 pg (N)
Linear range: 105-106 (halogens); 104-105 (N); 103.5-104(S)
Gases: Hydrogen (halogens and nitrogen); air (sulfur)
Temperature: 800-1000°C (halogens), 850-925°C (N), 750-825°C (S)

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 8. Mass Detector

 Mechanism:

Compounds are bombarded with electrons (EI) or gas molecules (CI). Compounds fragment
into characteristic charged ions or fragments. The resulting ions are focused and accelerated
into a mass filter. The mass filter selectively allows all ions of a specific mass to pass through
to the electron multiplier. All of the ions of the specific mass are detected. The mass filter
then allows the next mass to pass through while excluding all others. The mass filter scans
stepwise through the designated range of masses several times per second. The total
number of ions are counted for each scan. The abundance or number of ions per scan is
plotted versus time to obtain the chromatogram (called the TIC). A mass spectrum is
obtained for each scan which plots the various ion masses versus their abundance or
number.
Selectivity: compound gives fragments within mass range.
Sensitivity: 1-10 ng (full scan); 1-10 pg (SIM)
Linear range: 105-106
Gases: None
Temperature: 250-300°C (transfer line), 150-250°C (source)
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 Good Detector

Properties of a good detector.

1. High sensitivity.
2. Rapidly respond to concentration changes.
3. Large linear range.
4. Stable with respect to noise and drift.
5. Low sensitivity to variation in flow,
6. pressure and temperature.
7. Possible selectivity.
8. Produces an easily handled signal.
9. A temperature range from room temperature to at least 400 C.

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 GC Basic Components

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 Carrier gas .5

An inert gas, which is used to sweep a mixture to be separated

through a gas chromatograph , (helium, hydrogen, or nitrogen)

1. Push the sample through the gas chromatograph column

2. Clean out the gas chromatograph column after sample analysis

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 The carrier gas

ultra-pure and research-grade gases of up to 99.9999% (Grade

6.0) purity. the carrier gas system often contains a molecular
sieve to remove water or other impurities.

Linear Velocity (u)

Is the speed at which the carrier gas or mobile phase travels
through the column. The linear velocity is generally expressed in
cm/s
- The linear velocity is independent of the column diameter while
the flow rate is dependent on the column diameter.

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  Helium For carrier gas: 99.995%1 high purity, with less than 1.0 ppm each of
water, oxygen, and total hydrocarbons after purification.
Use water, oxygen, and hydrocarbon traps.
 Hydrogen For carrier or detector fuel gas: 99.995%1 high purity, with <
1.0 ppm of total hydrocarbons after purification.
Use water, oxygen and hydrocarbon traps.
 Air For detector fuel gas: 99.995%1 high purity.
Air compressors are not acceptable because they do not
meet pressure, water, and hydrocarbon requirements.
 Nitrogen For carrier or make-up gas: 99.995% high purity, with less than 1.0
ppm of total hydrocarbons after purification.
 Argon/5% Methane For ECD make-up gas: 99.995%1 high purity.

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 CAUTION

 Do not use liquid soap leak detectors to check for leaks. Liquid soap leak detectors may

contaminate you system. A mixture of 50% H2O/50% methanol or isopropyl

 alcohol may be used as a liquid leak detector.

 WARNING! Never use liquid leak detectors on or around electronic pneumatic circuits

Gamal A. Hamid 69
 Generators

 Nitrogen Generator
The nitrogen generator can also operate directly from the laboratory compressed air
supply. General contaminants are first removed with appropriate filters and adsorbents
and the purified air passes over layers of polymeric hollow fiber membranes through which
nitrogen selectively permeates.

 Hydrogen Generator
In the Packard Hydrogen Generator, hydrogen is generated electrolytically from pure
deionized water.
The electrolysis unit uses a solid polymer electrolyte and thus does not need to be supplied
with electrolytes, only the deionized water.

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 Chromatogram

Chromatogram

1. The data recorder plots the signal from the detector over time.

2. The retention time, is qualitatively indicative of the type of compound.

3. the area under the peaks or the height of the peak is indicative of the amount of each

component.

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 Retention Time (RT)

Retention time

• RT, is the time it takes for a compound to

travel from the injection port to the detector
• thousands of chemicals may have the same retention time, peak
shape, and detector response.
• For example, under certain conditions, DDT has the same retention
time as PCBs (polychlorinated biphenyls).

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 Retention Time Shifts

Retention Time Shifts

1. Different column temperature.

2. Different carrier gas flow rate or linear velocity.

3. Leak in the injector, especially the septum.

4. Contaminated column.

5. Change in the sample solvent.

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 SIMPLE CHECKS

1. Gases - pressures, carrier gas average linear velocity,

and flow rates (detector, split vent, septum purge).
2. Temperatures - column, injector, detector .
3. System parameters - purge activation times, detector attenuation, mass ranges, etc.
4. Gas lines and traps - cleanliness, leaks, expiration.
5. Injector consumables - septa, liners, O-rings and ferrules.
6. Sample integrity - concentration, degradation, solvent, storage.
7. Syringes - handling technique, leaks, needle sharpness, cleanliness.
8. Data system - settings and connections.

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 Sample Preparation

liquid-liquid extraction

liquid-liquid extraction is generally used to move

components from a less volatile liquid to a more

volatile liquid, e.g., from water to methylene chloride.

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 liquid-Solid extraction

The soxhlet extractor is used to extract organic

.compounds from solids

.The center chamber contains a porous paper thimble

Inside the thimble is the solid sample to be extracted.

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 Properties of injected sample

1. The sample should not be too large,

2 . The compounds are normally gases or they can be

Heated and vaporized into a gaseous state.

3. Non-selective detector responds to all compounds

4. Volatilized in a hot injection chamber

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 QA& QC Procedures

The standard sample must be analyzed with the same

instrument, under the same conditions, immediately before

and immediately after analyzing the unknown specimen.

If the resulting three spectral outputs do not agree, the

technician can not make a reliable identification of the

specimen based on the GC analysis.

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 Quantitative Analysis

Normalization method does response if:-

1. A portion of the injected sample is not eluted.

2. The detector does not respond to some component of
the sample.
3. Some component is not identified.
4. Some component is not resolved.
5. The response factor of some component is not known.
6. The area of some peak cannot be determined.

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Gamal A. Hamid 80
 Major Current GC Markets

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 Environmental

What is the environmental market?

1. Testing or commercial laboratories
2. Industrial laboratories
3. Government laboratories
4. Research institutes

Requirements of the applications

1. Drinking water
2. High sensitivity Waste
3. Sensitivity and selectivity Air
4. sample introduction

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 Clean water analysis

Pollutants in water
 Halocarbons
 Acid priority pollutants: phenols,
chlorophenols, nitrophenols
 Pesticides and PCBs
 Base neutral priority pollutants
 Polynuclear aromatic hydrocarbons

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 Analysis of Halocarbons in ground water

Column: DAI2ECD (MEGA) 30 m x 0.32 mm ID

Precolumn: 5 µm film thickness
Empity precolumn 10 m x 0.53 mm ID
OV1701 3 m x 0.53 mm ID
1 µm film thickness
Oven Program: 40°C for 2 min (rate 10°C/min)
to 70°C for 0,5 min (rate 3°C/min)
to 150°C for 0,5 min (rate 20°C/min)
to 310°C for 2 min
Injection Speed: 8 µl/sec
Solvent Delay Time: 17 sec
Pressure: 65 kPa, He, (constant pressure)
Extraction mode: 7 ml of sample in water
(in autosampler vial 10 ml)
with 3 ml of Diethyl ethere and mix

Peaks Compounds

0 DiChloroMethane
1 Chloroform
2 TriChloroethane
3 TriChloroEthylene
4 BromodiChloromethane
5 TetraChloroEthylene
6 DiBromoChloroMethane
7 Bromoformio
8 CarbonTetrachloride
9 DibromoMethane

Gamal A. Hamid 84
 PolyAromatic Hydrocarbons in water

Sample: River water spiked with 2 ppb PAHs (each)

Vial volume: 10 ml
Sample volume: 150 µl
Inj. speed: 5 µl/sec
Oven temp.: 65°C (4 min) up to 250°C (10 min)
then to 300°C (10 min) at 5°C/min
SVE delay: 30 sec
Precolumn: UNCORET
Column: 25 m x 0.32 mm ID, SE54, 0.45 µm film thickness
Detectors: PID (8.4 eV) and FID

Peaks Compounds

1 Naphtalene
2 Acenaphtylene
3 Acenaphtene
4 Fluorene
5 Phenanthrene
6 Anthracene
7 Fluoranthene
8 Pyrene
9 Benzo(a)anthracene
10 Chrysene
11 Benzo(b)fluoranthene
12 Benzo(k)fluoranthene
13 Benzo(a)pyrene
14 Indeno(1,2,3-cd)pyrene
15 Dibenzo(a,h)anthracene
16 Benzo(ghi)perylene

Gamal A. Hamid 85
 Chlorinated pesticides in ground water

Column: SE 52 MS 30 m x 0.25 mm, 0.25 µm f.t.

Precolumn: 2 m x 0.25 mm ID deactivated and
uncoated precolumn
Oven Program: 150°C for 1 min (rate 6°C/min)
to 300°C for 2 min
PTV Program: 35°C for 30 sec (rate 15°C/sec)
to 275°C for 2 min
Injection mode: Solvent split
Splitless Time: 1 min
Split Flow: 100 ml/min
Pressure: 95 kPa
Injection speed: 5 µl/sec
Extraction mode: 7 ml of sample in water
(in autosampler vial 10 ml)
with 3 ml of diethyl ether and mix

1 a-BHC 9 Dieldrin
2 b-BHC 10 p,p’-DDE
3 g-BHC 12 Endosulfan II
4 d-BHC 13 p,p’-DDD
5 Heptachlor 14 Endrin Aldheyde
6 Aldrin 15 Endossulfan Sulfate
7 Heptachlor Epoxide 17 Endrin Ketone
8 Endosulfan I 18 Methoxychlor

GC Analysis using PTV Solvent Split /LVI /ECD

Gamal A. Hamid 86
 Petrochemical and Gas

 Large replacement business

Refinery
Oil Industry
Gas suppliers
 Requirements of the applications
Multi-valves applications
Fastest possible cycle time
QC of gases: sensitivity
Customized software
Easy to use data handling and reporting

Gamal A. Hamid 87
 Mineral oil analysis SAMPLE
PREPARATION

TriPlus
syringe

Analysis of trace of mineral oil in ground water by petroleum

ether
in vial extraction and large sample volume injection
water

Solvent: Petroleum ether

C-14

C-12 C-16 Column: DB1, 30 m x 0.32 mm ID

C-18
0.25 µm film thickness
C-20
C-22 Precolumn: UNCORET
C-24
C-26 Inj. volume: 200 µl
C-28 Inj. speed: 5 µl/s
C-30
Inj. temp.: 45°C
C-32
C-10 Inj. pressure: 100 kPa
SVE time: 18 s

0 6 12 18 24 Time (min) Oven program: 45°C (3 min) to 320°C

(10 min) at 20°C/min

Gamal A. Hamid 88
 Mineral Oil Analysis

Sample: 0.2 µl of mineral oil

Column: 15 m x 100 µm ID,
SE54 0.15 µm f.t.
Temp. progr.:60°C to 350°C (3 min)
at 40°C/min
Carrier gas: Hydrogen at 0.35
ml/min
Inj. mode: constant flow
Inj. temp: split (1:400 split ratio)
Detector: 320°C
FID at 370°C

Narrow Bore Capillary Column

Gamal A. Hamid 89
 FID detection of Hydrocarbons

CH4 C3H8
Peak area reproducibility
Components CH4 C2H6 C3H8 iC4 nC4 iC5 nC5 C6+
C2H6
1998128 142669 215792 296627 308001 40857 41287 42361
i-C4H10 n-C 4H10
2007363 143282 216169 297831 309222 41377 41847 52223
2003870 143012 216065 297847 311117 41297 41791 52235
1997464 142518 215470 296846 308465 40967 41240 52361
Average 2001706 142870.3 215874 297287.8 309201.3 41124.5 41541.25 49795
Standard dev 4742.756 343.6145 312.7544 642.8102 1372.734 251.5784 322.1039 4956.393
Relative Standard dev % 0.24% 0.24% 0.14% 0.22% 0.44% 0.61% 0.78% 9.95%
i-C5H12
n-C5H12 n-C6H14

Gamal A. Hamid 90
 Food & Beverages

• Very extended market field

• No really regulated methods
• Ideal market to exploit the TRACE GC modularity
• Requirements of the applications
▫ QC of producers: Sensitivity and rapidity
▫ Multi detection capability
▫ Correct sample inlet (PTV-OC)
▫ Easy to use data handling and reporting

Gamal A. Hamid 91
 Determination of Fat Content of Foods

GC Analysis of FAME

Gamal A. Hamid 92
 Pharmaceutical

 Highly regulated market (pharmacopeia)

 Requires Validation package

 Requirements of the applications

• Limited instrument requirements SSL/NPD/FID

• Highly Automated market

• High sensitivity detectors

• A unified chromatography software

Gamal A. Hamid 93
 pharmaceutical

 Application focus

• OV solvent residual in tablets (20%)

• Drugs lab testing (50%)

Gamal A. Hamid 94
 Antihistaminic Drugs analysis
Inj. volume: 1 µl
Column: OV1, 25m x 0.32 mm ID, 0.15 µm f.t.
Oven: 140°C for 3 min
140°C to 230°C at 20°C/min
230°C for 2 min
230°C to 260°C at 20°C/min
260°C for 15 min
Inj. mode: splitless (250°C)
Carrier: Helium
Detector: NPD (275°C)z

Peaks Compounds
1 Pheniramine
2 Diphenhydramine
3 Tripelennamine
4 Cl. Pheniramine
5 Cyclizine
6 Carbinoxamine
7 Br. Pheniramine
8 Mianserine
9 Mepyramine
10 Promethazine
11 7-Methyl Mianserine (I.S)
12 Meclizine
13 Flunarizine
14 Cinnarizine

Gamal A. Hamid 95
 Forensic/Medical

 Application focus

• Blood Alcohols analysis (20%)

• Breathe oxygen purity (5%)

Gamal A. Hamid 96
 Thank you

Thanks

Gamal A. Hamid 97