H2615A Student

Introduction to
Capillary Gas Chromatography

Course Number H2615A
Student Manual
Introduction to
Capillary Gas Chromatography
H2615A
Student Manual
Manual Part Number H2615-90000

Printed in the USA Jan, 2001
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ii
Table Of Contents
INTRODUCTION TO CAPILLARY GC ....................................................................................1
INTRODUCTION .............................................................................................................................2
WHAT IS CAPILLARY GAS CHROMATOGRAPHY ............................................................................7
SAMPLE PREPARATION CONSIDERATIONS...................................................................................11
COLUMN CONSIDERATIONS ........................................................................................................12
BASIC COLUMN RESOLUTION..............................................................................................22
RESOLUTION EQUATION .............................................................................................................23
FLOW RATE/LINEAR VELOCITY AND RESOLUTION .....................................................................25
EFFICIENCY .................................................................................................................................29
TEMPERATURE AND RESOLUTION ...............................................................................................37
LIQUID PHASE AND RESOLUTION ................................................................................................42
SUMMARY...................................................................................................................................50
SAMPLE INTRODUCTION CONSIDERATIONS..................................................................53
TYPES OF INLET SYSTEMS ...........................................................................................................54
SPLIT/SPLITLESS INLET ...............................................................................................................57
ELECTRONIC PNEUMATIC FLOW CONTROL .................................................................................66
FLOW VS. TEMPERATURE ...........................................................................................................69
SPLIT/SPLITLESS INLET DESIGN ..................................................................................................74
INJECTION MODES ......................................................................................................................77
LINERS ........................................................................................................................................85
DETECTOR PARAMETERS .....................................................................................................87
TYPES OF DETECTORS .................................................................................................................88
DETECTOR SENSITIVITY ..............................................................................................................92
DETECTOR DYNAMIC RANGE......................................................................................................93
FID .............................................................................................................................................96
TCD............................................................................................................................................98
FID AND TCD COMPARISON ....................................................................................................100
ECD..........................................................................................................................................103
NPD..........................................................................................................................................104
EXERCISE 1: DETERMINING EFFICIENCY.....................................................................107
PART I: 30 M X 0.53MM X 0.88UM HP1 COLUMN ....................................................................108
PART II: 30 M X 0.32MM X 0.25UM HP 5 COLUMN ..................................................................111
EXERCISE 2: COMPARING COLUMN DIAMETER AND RESOLUTION ...................113
WORKSHEET .............................................................................................................................114
PACKED COLUMN ANALYSIS: 6' X 1/8" 5 % OV101 ON 80/100 CHROMOSORB.......................115
CAPILLARY COLUMN ANALYSIS: 30 M X 0.53 MM X 0.88 HP1 ...............................................116
CAPILLARY COLUMN ANALYSIS: 30 M X 0.32 MM X 0.25 UM HP5 .........................................117
EXERCISE 3: COMPARING COLUMN LENGTH AND RESOLUTION ........................119
WORKSHEET .............................................................................................................................120
EXERCISE 4: COMPARING COLUMN FILM THICKNESS AND RESOLUTION.......125
iii
WORKSHEET .............................................................................................................................126
EXERCISE 5: CALCULATING THE SPLIT RATIO ..........................................................131
WORKSHEET .............................................................................................................................132
SPLIT VENT FLOW = 44.8 ML/MIN ............................................................................................133
SPLIT VENT FLOW = 101.7 ML/MIN ..........................................................................................134
SPLIT VENT FLOW = 220 ML/MIN .............................................................................................135
EXERCISE 6: SPLIT AND SPLITLESS INJECTION .........................................................137
WORKSHEET .............................................................................................................................138
APPENDIX..................................................................................................................................141
REFERENCES .............................................................................................................................142
APPLICATION NOTES ................................................................................................................143
BIBLIOGRAPHY .........................................................................................................................154
EXERCISE ANSWERS .................................................................................................................161
iv
Introduction to Capillary GC
Introduction
Introduction
In This Section, You Will Learn:
• Course Description:
– The purpose of this one-day seminar is to introduce the analytical chemist to the
theoretical and practical principles of capillary gas chromatography.
• Course Goals:
– To determine what is needed in order to perform a GC analysis.
– To define resolution and column parameters for capillary columns in order to
achieve good resolution.
– To define the principles for sample introduction techniques (split/splitless).
– To define the principles for detection.
• Student Profile and Prerequisites:
– There are NO prerequisites for this course.
– This course is suitable for anyone desiring an introduction to the theory and
practice of capillary gas chromatography.
Figure 1
2
Introduction
Agenda
• Introduction: • Sample Introduction

– What is Capillary Gas Considerations:
Chromatography? – Split Injection Technique
– Sample Preparation – Electronic Pressure Controlled
Considerations Injection Technique
– Column Considerations – Splitless Injection Technique
• Basic Resolution Equation: • Detector Parameters:
– Column Efficiency Parameters – Definition of Detector Types
• Flowrate and Linear Velocity – Detector Response
• Column Diameter Characteristics
• Column Length – Flame Ionization Detector
• Carrier Gas Molecular Weight
– Capacity Parameters – Thermal Conductivity Detector
• Film Thickness – Electron Capture Detector
• Oven Temperature • Appendix
– Selectivity Parameters – Additional References
• Type of Stationary Phase
Figure 2
3
Introduction
Introduction
What is Capillary Gas Chromatography?
?
?
?? ?
Figure 3
4
Introduction
Typical Gas Chromatograph
MOL-SIEVE FIXED
TRAPS RESTRICTORS
RECORDER/
ELECTROMETER INTEGRATOR
INJECTION
PORT
REGULATORS
FLOW
CONTROLLER
DETECTOR
CARRIER GAS
HYDROGEN
COLUMN
AIR
Figure 4
5
Introduction
Definitions
• Gases:
– Carrier Gas – Pressurized gas used to transport the sample through the
system.
– Detector Gases – Support gases for certain detectors (i.e., FID).
• Sample Introduction:
– Introduces the sample to the carrier gas stream with minimal disruption of
the gas stream.
• Column:
– Achieves separation of the components in the sample.
• Detector:
– Recognizes and responds to sample components as the elute from the
column.
• Data Acquisition:
– Converts the detector signal to a picture chromatograph and provides
manual or automated determination of the identity and amounts of the
sample components.
Figure 5
6
What is Capillary Gas Chromatography
What is a Chromatograph?
Chromatograph and Report generated by the 3365 ChemStation.
Capillary Column Analysis:

30 M x 0.32 mm x 0.25 uM HP5
9
Column Flowrate = 1 mL/min 1 2 6 7 10 11 12
Linear Velocity = 20.5 cm/sec 5
4
Temperature Program:
Isothermal 160 3
Split Mode: 8
Split Ratio = 100:1
FID
1 uL Column Checkout Sample
Area Percent Report

Pk# Ret. Time Area Height Type Width Area% Name
1 2.442 62321 45133 BV 0.022 0.2127 Pentane
2 2.556 2.9045E+07 1.87002E+07 VV 0.024 99.11066 Solvent
3 2.672 8303 5036 VB 0.026 0.0283+
4 3.100 10129 7143 BB 0.023 0.0346 Undecane
5 3.511 14978 7438 BB 0.032 0.0511 4-Chlorophenol
6 3.816 16871 9417 BB 0.028 0.0576 1-Decylamine
7 4.156 17124 9425 BB 0.029 0.0584 Tridecane
8 4.359 7748 3907 BB 0.031 0.0264 Methyl caprate
9 5.179 33486 14578 BB 0.046 0.1143 Tetradecane
10 6.315 27045 9249 BB 0.046 0.0923 Acenaphthylene
11 6.542 29540 8682 BB 0.053 0.1008 1-Dodecanol
12 6.789 34293 11407 BB 0.047 0.1170 Pentadecane
Total area = 2.9307E +07
Figure 6
7
Typical Chromatograph from the 3396 Integrator
RUN# 54 JAN 3, 1901 00:56:26
SAMPLE NAME: BGC SAMPLE# 1

AUTO TEST
AREA%
RT AREA TYPE WIDTH AREA%

1.178 94134 PB .010 .11476
1.234 4920 BP .011 .00600
1.282 81205504 SPB .016 99.00070
1.361 2650 BP .011 .00323
1.397 24940 PP .019 .03041
1.524 5191 PB .012 .00633
1.952 36455 PB .015 .04444
2.500 50784 PB .020 .06191
2.960 57560 PB .023 .07017
3.530 62750 PB .028 .07650
3.860 29708 PB .031 .03622
5.242 120098 PB .045 .14642
6.715 107378 PB .055 .13091
7.229 99861 PB .062 .12174
8.160 123337 BB .075 .15036
TOTAL AREA=8.2025E+07
MUL FACTOR=1.0000E+00
8
Figure 7
8
What Must Be Done in Order to Perform a GC

Analysis?
?
?
? ?
?
Figure 8
9
What will Be Discussed in This Course
Identification of what must be done; Not how to perform

Operational Tasks.
• Topics Include:
– Sample Preparation Considerations
– Choosing a Column for Best Resolution
– Identifying Choice of Inlets
– Identiying Detectors
• Topics NOT Included:

– How to Install a Column
– How to Set Flows
– How to Calibrate
– How to Use an Auto Injector
10
Figure 9
10
Sample Preparation Considerations
Sample Preparation Considerations
Capillary Columns Require CLEAN SAMPLES!

What are some sample preparation methods?
• ____________ ("Dilute and Shoot")

• ____________ Solution
Centrifugation
Filtration
• ____________
Ion Exchange, Adsorption Columns
Other Solid Phase Extraction
Separatory Funnel
Supercritical Fluid Extraction
Headspace
• _____________
Thermal Desorption
Headspace
• ____________
Purge and Trap
• ____________
Pyrolysis
Derivatization
• Have as ____________ a Sample as Possible.

11
Figure 10
11
Column Considerations
Columns
What is the primary
function of the column?
?? ??
?
12
Figure 11
12
Column Selection Techniques
The following are the most common methods used for column
selection:
– Tray a column that is handy.

– Ask a colleague for advice.
– Look for a similar application that has already been published.
– In in doubt, use a non-polar capillary column such asm HP1 or HP5.
These approaches are good starting points, but one must optimize
performance.
13
Figure 12
13
Example Applications
Type of Column
Carrier Conditions
Oven Conditions
Injection Parameters
Detector Parameters
Sample Information
14
Figure 13
14
What are the Column Types?

Open Tubular (Capillary)
Wall Coated
Open Tube
Porous Layer 30 Meter X 0.53 mm X 0.88um HP1

Open Tube
Length Diameter Film Type

Thickness of Phase
Packed
Conventional
Packed and Porous
Micro Packed Layer
Bead
6 Feet X 1/8 inch 5% OV101 on 80/100 Chromosorb
Length Diameter Concentration Type of

and Type of Solid Support
Phase
15
Figure 14
15
Packed Column
Packed Column: 6’ x 1/8” 5% OV101
on 80/100 Chromosorb
Capillary Column Analysis: 1 2

4
Column Flowrate = 30 mL/min 7
Linear Velocity = 12.4 cm/sec
6 9
5
Isothermal 130 11 & 12
10
Split Mode: 8
Split Ratio = 100:1
FID
Area Percent Report

1 0.246 2879398 4458532 BV 0.015 0.2317 Pentane
2 0.341 1.22622E+09 8.10852E+08 HBS 0.026 98.6695 Solvent
4 1.006 823259 279443 BBT 0.046 0.0662 Undecane
5 1.361 916089 177078 BBT 0.073 0.0737 4-Chlorophenol
6 2.512 1387522 196260 BV 0.106 0.1116 1-Decylamine
8 2.630 749162 97326 VB 0.113 0.0603 Methyl caprate
7 4.12 2650317 232666 BV 0.177 0.2133 Tridecane
9 4.505 2331063 193209 VB 0.187 0.1876 Tetradecane
10 5.678 1879881 106858 BV 0.253 0.1513 Acenaphthylene
11&12 6.830 2807565 146329 VB 0.297 0.2259 1-Dodecanol & Pentadecane
16
Figure 15
16
Capillary Column – 0.53mm ID

30 M x 0.53 mm x 0.88 uM HP1 1 2
Column Flowrate = 2.6 mL/min 9
12
Isothermal 180 7&8 10 11
5
Split Mode: 4
6
Split Ratio = 39:1
FID
Area Percent Report

1 2.541 333138 156491 BV 0.033 0.7688 Pentane
2 2.711 4.24499E+07 1.81871E+07 PV 0.036 97.9577 Solvent
4 3.438 27293 11612 BB 0.0630 0.0630 Undecane
5 3.743 44075 13854 BB 0.1017 0.1017 4-Chlorophenol
6 4.206 38866 12775 BB 0.0897 0.0897 1-Decylamine
7&8 4.670 71919 16219 BB 0.1660 0.1660 Tridecane & Methyl caprate
9 5.772 96872 25091 BB 0.2235 0.2235 Tetradecane
11 6.808 91419 16880 VB 0.2110 0.2110 1-Dodecanol
12 7.420 102251 20686 BB 0.2360 0.2360 Pentadecane
17
Figure 16
17
Capillary Column – 0.32mm ID

30 M x 0.32 mm x 0.25 uM HP5
1 2 6 9 11 12
Column Flowrate = 1 mL/min 7 10
Linear Velocity = 20.5 cm/sec 4 5
3
Isothermal 160
Split Mode: 8
Split Ratio = 100:1
FID
Area Percent Report

1 2.442 62321 45133 BV 0.022 0.2127 Pentane
2 2.556 2.9045E+07 1.87002E+07 VV 0.024 99.11066 Solvent
3 2.672 8303 5036 VB 0.026 0.0283+ Impurity
4 3.100 10129 7143 BB 0.023 0.0346 Undecane
5 3.511 14978 7438 BB 0.032 0.0511 4-Chlorophenol
6 3.816 16871 9417 BB 0.028 0.0576 1-Decylamine
7 4.156 17124 9425 BB 0.029 0.0584 Tridecane
9 5.179 33486 14578 BB 0.046 0.1143 Tetradecane
11 6.542 29540 8682 BB 0.053 0.1008 1-Dodecanol
12 6.789 34293 11407 BB 0.047 0.1170 Pentadecane
18
Figure 17
18
What Does the Column Provide?
____________ is a measure of the ability of a column to separate into two

peaks. Separation of compounds , and
Flow
A
Let’s look at how the separation D
occurs.
19
Figure 18
19
A Trip Down Bourbon Street
Non-Drinker: 1 Bar in 1 minutes

Bourbon Drinker: 1 Bar in 2 minutes
Hurricane Drinker: 1 Bar in 4 minutes
Bourbon Street with 4 Bars

Joe's Place Howard's Two Guys Sam's Spirits
Time for Non-Drinker to Elute at End of Street: ____ minutes.
Time for Bourbon Drinker to Elute at End of Street: ____ minutes.
Time for Hurricane Drinker to Elute at End of Street: ____ minutes.
Non-Drinker Bourbon Drinker Hurricane Drinker

RT = ______ RT = ______ RT = ______
20
Figure 19
20
21
Basic Column Resolution
Resolution Equation
Resolution Equation
Basic Resolution Equation
R=
n k
α-1
4
1+k α
Column Retention Selectivity
Efficiency (Capacity)
FACTORS AFFECTING
Flowrate / Linear Velocity Film Thickness Type of Stationary Phase

Column Diameter Oven Temperature
Column Length
Carrier Gas Molecular Wt.
Figure 20
23
Resolution Equation
Basic Resolution Equation (cont.)
R=
n k
α- 1
4 1+k
α
FACTORS AFFECTING

Column Length
Figure 21
24
Flow Rate/Linear Velocity and Resolution
Chromatograms Using Different Flow

Rates/Linear Velocities

30 M x 0.53 mm x 0.88 uM HP1 1 8
2
Column Flow rate = 4.5 mL/min 5 9
Linear Velocity = 34 cm/sec 4 6 11
3 10
Isothermal 160
7
Split Mode:
Split ratio = 23:1
FID
Pk# Ret. Time Name

1 1.477 Pentane
2 1.609 Solvent
3 2.333 Undecane
4 2.638 4-Chlorophenol
5 3.143 1-Decylamine
6 3.681 Tridecane
7 3.738 Methyl caprate
8 4.970 Tetradecane
9 5.823 Acenaphthylene
10 6.009 1-Dodecanol
11 6.982 Pentadecane
Figure 22
25

Rates/Linear Velocities (cont.)

30 M x 0.53 mm x 0.88 uM HP1
Column Flow rate = 10.3 mL/min 12
Linear Velocity = 78 cm/sec 4 8
9
5 6&7
Isothermal 160 3 10 11
Split Mode:
Split ratio = 11:1
FID
Pk# Ret. Time Name

1 0.640 Pentane
2 0.695 Solvent
3 1.012 Undecane
6 1.597 Tridecane
7 Methyl caprate
8 2.157 Tetradecane
5
Figure 23
26

Rates/Linear Velocities (cont.)

1 2
30 M x 0.53 mm x 0.88 uM HP1
Column Flow rate = 28 mL/min 4 8
9
Linear Velocity = 213 cm/sec 6&7
5 10 11
Temperature Program: 3
Isothermal 160
Split Mode:
Split ratio = 4.5:1
FID
Pk# Ret. Time Name

1 0.235 Pentane
2 0.254 Solvent
3 0.372 Undecane
6 0.589 Tridecane
7 Methyl caprate
8 0.793 Tetradecane
Figure 24
27
Back to Bourbon Street

Column Flowrate or Linear Velocity
Bourbon Street with 4 Bars

Figure 25
28
Efficiency
Efficiency
Efficiency – Sharp Peaks

Solute
Separation efficiency is a measure of the broadening of
the solute plug as it travels the length of the column.
Start
(Solvent)
Wh = .074
Inert Gas
t m t 'R
(1.477) t R (6.982) Time
We would like to know the actual time the

component spends in the stationary phase.
t R' = t R - tm t R' = 6.982 - 1.477
= 5.51
t R' 2
n = 5.545 n = effective theoretical plates
Wh
n = 30,743
Let's relate n to the length of the column.
n 30743
Plates per meter (N) = = = 1024
or L 30
L (mm)
Height equivalent to a theoretical plate (HETP) = = 0.98 n
Thus, the more efficient the column the bigger the "N" , the smaller the "HETP".
Figure 26
29
Efficiency
Efficiency and Carrier Gas Linear Velocity
B
HETP = A + +Cu
u
HETP
B{ }
MOLECULAR C RESISTANCE TO MASS TRANSFER
DIFFUSION }
A EDDY DIFFUSION
u opt u
2
Flowrate (ml/min) = r u 60 π
r = Column radius in cm
u = Average linear velocity in cm/sec
col length (cm)

u=
R.T. (sec) of non-retained species
The minimum of the curve represents the smallest

HETP (or largest plates per meter) and thus the
best efficiency. "A" term is not present for
capillary columns.
9
Figure 27
30
Efficiency
Optimum Flowrate Related to Column Diameter

Generally, the following guidelines may be used for finding the optimum
values for a particular column:
Packed Columns
Optimum Carrier Optimum Carrier

Column Diameter Flowrate Linear Velocity
1/4" 50-60 ml/min 2.6 - 3.2 cm/sec
1/8" 20-30 ml/min 4.2 - 6.3 cm/sec
Capillary Columns
Optimum Carrier Optimum Carrier

Column Diameter Flowrate Linear Velocity
Series 530 mµ (megabore) 3-5 ml/min 22 - 38 cm/sec
320µ m (wide bore) 1-2 ml/min 20 - 41 cm/sec
200 µ m (narrow bore) .4-.6 ml/min 21 - 32 cm/sec
100µ m (high speed) .2-.5 ml/min 42 - 106 cm/sec
10
Figure 28
31
Efficiency
Column Diameter vs. Efficiency
9000
5000
Efficiency
4000
3000
1800
1200
(n/m)
0.1 0.2 0.25 0.32 0.75 2
0.53 (packed)
Column Internal Diameter (mm)
11
Figure 29
32
Efficiency

Column Diameter vs. Efficiency
Version 1: 4 Bars on Narrow Street
Joe's Place Tw o G uys
H ow ard's Sam's Spirits
Version 2: 4 Bars on Wide Street

H ow ard's Sam's Spirits
12
Figure 30
33
Efficiency
Increased Sensitivity with Capillary Columns
Packed Columns Capillary Columns
Area = 2600 Area = 2600

Height = 5 S/N = 5 Height = 10 S/N = 10
Noise = 1 Noise = 1
Sensitivity = Concentration/Unit Time
13
Figure 31
34
Efficiency
n k α -1
R=
4 1+k α
FACTORS AFFECTING

Column Length
An "R" value can be calculated:
1.18 (RT - RT2) 1

R=
(W 1+ W 2 )
R = 1.5 Represents Baseline Resolution
14
Figure 32
35
Efficiency

Film Thickness
Version 1: 4 Bars
Howard's Sam's Spirits
Version 2: 4 Bars - Each 3 Times Larger
Howard's Sam's Spirits
15
Figure 33
36
Temperature and Resolution
Oven Temperature
Isothermal 130 degrees

30 M x 0.32 mm x 0.25 uM HP5
Column Flowrate = 1 mL/min 1
2
6
Constant Flow On 4 5
7
Temperature Program: 10 11 12
Isothermal 130
Split Mode:
8
Split ratio = 100:1
FID
Area Percent Report

1 2.349 66784 53782 BV 0.020 0.2090 Pentane
2 3.871 3.1668E+07 2.10801E+07 BBA 0.023 99.1278 Solvent
4 3.871 10949 6531 BB 0.027 0.0343 Undecane
5 4.943 16594 6390 BB 0.041 0.0519 4-Chlorophenol
6 5.853 18685 7146 BB 0.041 0.0585 1-Decylamine
7 6.963 18975 6202 BB 0.048 0.0594 Tridecane
9 10.304 36848 7892 BB 0.073 0.1153 Tetradecane
11 14.178 30476 4662 BB 0.103 0.0954 1-Dodecanol
12 15.996 37948 5207 BB 0.115 0.1188 Pentadecane
Efficiency (based on C14 peak) = 2195 plates per meter
16
Figure 34
37
Oven Temperature (cont.)


30 M x 0.32 mm x 0.25 uM HP5 9 12
Column Flowrate = 1 mL/min 1 2 6 7 10 11
Constant Flow On
Isothermal 160 8
Split Mode:
Split ratio = 100:1
FID
Area Percent Report

1 2.442 62348 45138 BV 0.022 0.2130 Pentane
2 2.556 2.90175E+07 1.87003E+07 VBA 0.024 99.1321 Solvent
4 3.100 10129 7143 BB 0.023 0.0346 Undecane
5 3.511 15015 7442 BB 0.032 0.0513 4-Chlorophenol
6 3.816 16871 9417 BB 0.028 0.0576 1-Decylamine
7 4.156 17543 9474 BB 0.029 0.0599 Tridecane
9 5.179 33486 14578 BB 0.036 0.1144 Tetradecane
11 6.542 29534 8681 BB 0.053 0.1009 1-Dodecanol
12 6.789 34293 11407 BB 0.047 0.1172 Pentadecane
17
Figure 35
38
Oven Temperature (cont.)


30 M x 0.32 mm x 0.25 uM HP5
Constant Flow On 10
12
6 7
Isothermal 200
5
Split Mode: 4
Split ratio = 100:1 8
FID
Area Percent Report

1 2.571 90685 59862 BV 0.024 0.3578 Pentane
2 2.633 2.50872E+07 1.50586E+07 VB 0.026 98.9838 Solvent
4 2.841 8765 6242 BB 0.022 0.0346 Undecane
5 2.997 13048 6939 VV 0.030 0.0515 4-Chlorophenol
6 3.082 14917 9536 VV 0.025 0.0589 1-Decylamine
7 3.171 15333 10241 VV 0.024 0.0605 Tridecane
9 3.454 29065 18233 BB 0.025 0.1147 Tetradecane
11 3.862 29761 17018 VB 0.028 0.1174 1-Dodecanol
12 4.014 25502 11379 BV 0.035 0.1006 Pentadecane
18
Figure 36
39
Temperature Programming
Rate Time 2
C
2 min
Min
Time 1 10 C Temp 2
Capillary Column Analysis: 0 min min 170
30 M x 0.32 mm x 0.25 uM HP5 Temp 1
130
Column Flowrate = 1 mL/min
Initial Temp 130 1 2
9
12
Initial Time 0 min 10
Rate 10 7
11
6
Final Temp 170
5
Final Time 2 min 4
Split Mode: 8
Split ratio = 100:1
FID
Area Percent Report

1 1.842 306172 350394 BV 0.019 0.6820 Pentane
2 1.972 4.4062E+07 3.51403E+07 BV 0.033 98.1430 Solvent
4 2.636 269555 27802 BB 0.016 0.0600 Undecane
5 3.071 41444 32610 BB 0.020 0.0923 4-Chlorophenol
6 3.375 44080 38682 BB 0.030 0.0982 1-Decylamine
7 3.687 47924 41829 BB 0.018 0.1067 Tridecane
9 4.451 92643 68565 BB 0.021 0.2064 Tetradecane
11 5.276 82445 44760 VB 0.029 0.1836 1-Dodecanol
12 5.462 94778 56319 BB 0.027 0.2111 Pentadecane
19
Figure 37
40
R=
n k α -1
α
4 1+k

FACTORS AFFECTING

Column Length
α = Relative Retention of a Critical Pair of

Sample Components
1
= t R,j t 1 R,j > t 1 R,i
α 1
t R,i
α > 1 Indicates that Separation can be Achieved
20
Figure 38
41
Liquid Phase and Resolution
Liquid Phase Selectivity

Methyl Silicone (HP-1)

10 M x 0.53 mm x 2.65 uM HP1 (Methyl Silicone)
5
Temperature Program: 4 6
Isothermal 130
9 10
Split Mode: 7
12
FID 8
Area Percent Report

1 0.604 133320 227653 BV 0.010 0.3039 Pentane
2 0.881 4.29654E+07 3.00866E+07 BBA 0.024 97.9490 Solvent
4 2.859 37894 11253 BV 0.053 0.0864 Undecane
5 3.774 60737 14524 BB 0.066 0.1385 4-Chlorophenol
6 5.360 70988 11414 BB 0.098 0.1618 1-Decylamine
7 7.334 68144 7811 BV 0.137 0.1553 Tridecane
9 12.102 127604 8955 BB 0.223 0.2909 Tetradecane
11 16.068 112143 6044 BB 0.288 0.2557 1-Dodecanol
12 20.157 128763 5433 BB 0.369 0.2935 Pentadecane
21
Figure 39
42
Liquid Phase Selectivity (cont.)

5% Phenyl Methyl Silicone (HP-5)

10 M x 0.53 mm x 2.65 uM HP5 (5% Phenyl Methyl Silicone)
Column Flowrate = 1 mL/min
1
5
6
Isothermal 110
9
Split Mode: 7 10
Split ratio = 33:1
11 12
FID 8
Area Percent Report

1 0.618 154322 233139 BV 0.011 0.2751 Pentane
2 0.923 5.52701E+07 2.60518E+07 BBA 0.037 98.5360 Solvent
4 2.861 33818 9229 BB 0.058 0.0603 Undecane
5 4.445 53379 10021 BB 0.082 0.0952 4-Chlorophenol
6 5.777 62584 8900 BB 0.102 0.1116 1-Decylamine
7 7.420 57894 6349 BB 0.141 0.1032 Tridecane
9 12.336 111045 7405 BB 0.230 0.1980 Tetradecane
11 18.037 94467 4603 BB 0.333 0.1738 1-Dodecanol
12 20.709 112933 4515 BB 0.393 0.2013 Pentadecane
22
Figure 40
43
Liquid Phase Selectivity (cont.)

50% Phenyl Methyl Silicone (HP-17)

15 M x 0.53 mm x 2.0 uM HP17 ( 50% Phenyl Methyl Silicone)
Column Flowrate = 2.8 mL/min
1
2
Isothermal 110 4
9
Split Mode: 7
12
5
FID 11
8 10
Area Percent Report

1 0.549 161267 275185 BV 0.010 0.2074 Pentane
2 0.755 7.63174E+07 6.62005E+07 BBS 0.030 98.5725 Solvent
4 1.301 66872 35187 BB 0.030 0.0860 Undecane
7 3.014 117546 27749 BB 0.066 0.1512 Tridecane
6 3.530 106182 21612 BB 0.075 0.1365 1-Decylamine
9 4.976 223142 33084 BV 0.106 0.2869 Tridecane
5 5.137 97490 17999 VB 0.083 0.1254 4-Chlorophenol
12 8.462 227177 20290 BB 0.177 0.2921 Pentadecane
11 12.847 186844 11987 BB 0.245 0.2403 Dodecanol
23
Figure 41
44
Common Stationary Phase Coatings for

Capillary Columns
BONDED STATIONARY PHASES SPECIALTY PHASES
Applications HP Phases Applications HP Phases

Amines, HP-1 or Ultra 1 Purgeable Organics HP-VOC
Hydrocarbons,
Volatile Halogenated HP-624
Pesticides, Chlorinated Pesticides HP-608
PCBs, Phenols,
Sulfur Compounds
Alkaloids, Drugs, HP-5 or Ultra 2

Fatty Acid Methyl, CLASSIC PHASES (NONBONDED)
Esters,
Halogenated
Compunds
Drugs, Glycols, Applications HP Phases
HP 50+ Amino Acid HP-101
Pesticides, Derivatives,
Steroids Essential Oils
Acids, Alcohols, HP-FFAP Drugs, Glycols, HP-17
Aldehydes, Pesticides,
Acrylates, Steroids
Ketones, Nitriles
Alcohols, HP-20M
Alcohols, Free HP-INNO Wax Free Acids,
Acids, Aromatics, Essential Oils,
Essential Oils, Ethers, Glycols,
Solvents Solvents
24
Figure 42
45
46
Porous Layer Open Tubular Column
Analysis of Low Molecular Weight Substances or Inert Gases at Ambient

Temperature:
Specifications AI 2O 3/KCI AL 2O 3/Na SO

2 4
MolSieve A PoraPLOT Q PoraPLOT S PoraPLOT U CarboPlot P7
Applications C 1-C 10 High Permanent Alcohols, Hydro- Polar He, N 2,

Hydro- Selectivity gases, He, polar and carbons, volatiles, O 2 , CO,
carbons; towards Ne, Ar, O , apolar ketones, nitriles, CO ,
2 2
ppm C -C C N , CH , volatiles esters nitro com- C -C
2
in C -C1 2 4
isomers CO, C H4 , in water; pounds, 1 2
1 4
CD , C2 D6 hydro- alcohols,
hydrogen
4 2 6 carbons aldehydes
isotopes gases, ethane/
solvents ethylene,
ppm water,
'wet'
samples
25
Figure 43
Analysis of low molecular weight substances or inert gases at ambient

temperature.
47
Comparison of Plot and Packed Columns

Permanent Gases
1. Hydrogen 5% 2
2. Nitrogen 48.5%
3. Oxygen 13%
4. Argon 0.5%
5. Carbon Monoxide 33% 5
3 Packed
Column
1 4
9 min
Column: 6' x 1/8" SS packed with HayeSep A 80/100 mesh
Oven: 25 C o
Detector: TCD
Flow: He 23 cc/min
Sample: 25 microliters Air plus hydrogen and Carbon Monoxide
Analysis of Laboratory Air

Column: 25 M x 0.32 mm fused silica PLOT
Molsieve 5A (30.0 mm)
(Part No. 19091P-MS2)
Temperature: 30 C o
Carrier Gas: H2, 55kPa (0.55 bar, 8 psi), 56 cm/s
Injector: Splitter, 200 ml/min
T = 150 C o
Detector: TCD o 2 3
T = 180 C
Sample size: 30 ul
1. Argon
2. Oxygen Plot
3. Nitrogen
Column
1
o 8 min
26
Figure 44
48
R=
n k
α -1
4 1+k
α
FACTORS AFFECTING

Column Length
27
Figure 45
49
Summary
Summary
Summary Relationships
1. Using capillary columns requires the use of very ____________ samples.

2. The ____________ the flowrate or linear velocity, the shorter the retention
time.
3. The ____________ the column diameter, the lower the optimum flowrate or
linear velocity.
4. The ____________ the column diameter, the more efficient the column.
5. Increased efficiency results in ____________ peaks and usually better
resolution.
6. Optimum ____________ or _____________ is affected by the type of
carrier gas used.
7. Detector sensitivity is _____________ with more narrow diameter columns
because the signal to noise ratio is increased.
8. Temperature Programming often improves the efficiency and
____________ the time of analysis.
28
Figure 46
50
Summary
Type of Column
Carrier Conditions
Oven Conditions
Detector Parameters
Sample Information
29
Figure 47
51
Summary
52
Sample Introduction Considerations
Types of Inlet Systems
Sample Introduction
Purpose:
To introduce the sample on to the column in the vapor state.
• Syringe Injection:
– Manual injection
– Autosampler injection
• Valve Injection
– Gas sampling valves
– Liquid sampling valves
• Auxiliary Sampling Devices
– Purge and Trap
– Headspace
Figure 48
54
Purpose:
To allow the insertion of a sample into the gas chromatograph in a repeatable,
reproducible manner. The sample should be representative of the bulk, and
unless specifically desired, should be inserted without chemical change.
– Packed column inlet

– Septum-purged packed column inlet
– Split/splitless capillary inlet
– Split-only capillary inlet
– Electronic pressure controlled (EPC) cool on-column
– EPC Purged packed inlet
– EPC Capillary split/splitless inlet
Inlet design must consider the characteristics of capillary columns:

– High efficiency
– Low sample capacity
Figure 49
55

Four buses of tourists unload at the same time.
Canal Street
Split Vent
Bourbon Street Too many people would overload

Bourbon Street. Therefore, a large
proportion of the tourists go down
Canal Street.
Column
4
Figure 50
56
Split/Splitless Inlet
Split/Splitless Capillary Inlet

SEPTUM
VALVE
FLOW CONTROLLER (SEPTUM)
PURGE VENT
TOTAL FLOW
SPLIT VENT
BACK
(INLET) PRESSURE
PURGE VALVE REGULATOR
COLUMN
HEAD
COLUMN PRESSURE
SEPTUM
TOTAL FLOW PURGE
SPLIT VENT
PURGE VENT
Column flow is set by altering COLUMN HEAD PRESSURE.
SEPTUM PURGE should be set to 2-3 mL/min.

SPLIT VENT flow is TOTAL FLOW minus COLUMN FLOW and
SEPTUM PURGE flow.
Changing TOTAL FLOW should NOT change COLUMN HEAD PRESSURE

or SEPTUM PURGE flow.
Figure 51
57
Capillary Flow Diagram:

Pre-Injection
SEPTUM
(SEPTUM)
2 mL/min PURGE VENT
TOTAL FLOW
50 mL/min
SPLIT VENT
(INLET)
48 mL/min
PURGE VALVE
47.4 mL/min
= CARRIER GAS
LINER
SEAL (Small
grooves in the
seal allow the
0.6 mL/min split to occur.)
COLUMN
Figure 52
58

Sample Injection
(SEPTUM)
PURGE VENT
TOTAL FLOW
SPLIT VENT
(INLET)
PURGE VALVE
= LIQUID SAMPLE
= CARRIER GAS
COLUMN
Figure 53
59

Sample Vaporization
(SEPTUM)
PURGE VENT
TOTAL FLOW
SPLIT VENT
(INLET)
PURGE VALVE
Vaporization takes place when sufficient

thermal energy is transferred to the sample.
= CARRIER GAS
= SAMPLE MOLECULES This can occur in the carrier gas, but is
more likely upon contact with a solid
= SOLVENT MOLECULES surface, such as the liner or mixing medium.
COLUMN
Figure 54
60

Sample/Carrier Mixing
(SEPTUM)
PURGE VENT
TOTAL FLOW
SPLIT VENT
(INLET)
PURGE VALVE
For the concept of SPLIT RATIO to be

valid, the sample (solvent + analyte)
must be mixed with the carrier gas to
= CARRIER GAS give a homogeneous mixture.
= SAMPLE MOLECULES
= SOLVENT MOLECULES At the bottom of the injection port

a small part of this mixture will
transfer to the column, while the
bulk of the mixture will leave the
inlet via the SPLIT VENT.
COLUMN
SPLIT RATIO = COLUMN FLOW + SPLIT VENT FLOW

COLUMN FLOW
Figure 55
61

Liner Overload
(SEPTUM)
PURGE VENT
TOTAL FLOW
SPLIT VENT
(INLET)
PURGE VALVE
A large injection of a solvent with a

large expansion volume can cause an
overload of the injection port liner.
= CARRIER GAS
This can result in loss of sample out
= SAMPLE MOLECULES the PURGE VENT as well as
= SOLVENT MOLECULES contamination of the in-coming carrier
gas line.
COLUMN
10
Figure 56
62
Split Ration Calculation

Split Ratio = Split Vent Flow + Column Flow
Column Flow
COLUMN
B HEAD
PRESSURE
SEPTUM
TOTAL FLOW PURGE
A
SPLIT VENT PURGE VENT
D C
A B C D
Column Total Column Septum Split Split
I.D. (um) Flow Flow Purge Flow Ratio
200 100 0.5 2.0 97.5 196:1
320 100 1.0 2.0 97 98:1
530 100 3.0 2.0 95 33:1
Split Vent Flow = (Split Ratio)(Column Flow) - Column Flow
11
Figure 57
63
Capillary Liners
Untreated Liners
Split/Splitless 4-mm id, 1000 ul nominal volume
Borosilica glass (untreated) with silanized glass wool plug
PN 19251-60540 Split and splitless modes, especially recommended
for rapid injections with the HP Automatic Sampler
(Univeral Liner)
Splitless 2-mm id, 250 ul nominal volume
PN 18740-80220 quartz glass (untreated), open tube
Splitless mode for slow injections
(manual and HP7671/7672 automatic samplers)
small sample volumes (< 1 ul)
and higher boiling point solvent systems
Deactivated Liners
Packed, tapered 4-mm id, 900 ul nominal volume
PN 5062-3587 Borosilica glass (deactivated), silanized glass wool plug
(deactivated)
Split and splitless modes,
can be self-packed
Unpacked, tapered 4-mm id,900-ul nominal volume
PN 5181-3316 borosilicate glass (deactivated)
can be self-packed
Dual-tapered 4-mm id, 800 ul nominal volume
but preferred for splitless
TREAT AS ULTRA CLEAN PART!

NOTE: See Supplies Catalog for latest variety of liners.
12
Figure 58
64
Split Injection and Selective Inlets
Split injection may be used with:

– Valves
– Head Space Autosamplers
– Thermal Desorbers
– Purge and Trap Samplers
– Analytical Prolyzers
For additional information on these techniques, see:

GC Inlets – An Introduction, by Mathew Klee, Chapters 9-13.
13
Figure 59
65
Electronic Pneumatic Flow Control
Standard Split/Splitless Capillary Inlet with

Electronic Pressure Control (EPC)
This inlet has the same features as the

SPLIT PROGRAMMABLE standard inlet plus the following:
PRESSURE
Pressure Control:
Programming: 3 ramps, 0.01-99
psi/min.
TOTAL FLOW Range: 1-100 psi (7-689 kPa) digital
INCR
readout of head pressure.
Flow Range: 0-450 mL/min.
SPLIT/SPLITLESS SEPTUM PURGE
Constant Flow Mode: Inlet pressure is
INLET VENT VENT adjusted real time to maintain constant
INJECTION PORT volumetric flow at column outlet.
14
Figure 60
66
Type of Column
Carrier Conditions
Oven Conditions
Detector Parameters
Sample Information
15
Figure 61
67
The Analysis Process

Advantages of EPC for GC Inlets
Sample Preparation
Pressure programming at
injection can enhance
Sample Introduction transfer to the column
Pressure/temperature
programming can
Separation optimize separations,
reduce analysis times
Detection Constant flow can

stablize detector
response, improve peak
shapes for quantitation
Data Reduction
16
Figure 62
68
Flow Vs. Temperature
Flow vs. Temperature

30M x 0.32 x 0.25uM HP-5
Constant Flow Mode
FLOW (mL/min)
Constant Pressure Mode
FLOW (mL/min)
1.0
1.0 5 psi .8
.8 .6 0.92 mL/min
.6
.4
.4
.2
.2
50 100 150 200 250 300
50 100 150 200 250 300 TEMPERATURE
TEMPERATURE
PRESSURE (psi)
PRESSURE (psi)
10
10
8
8
6
6
4
4
2
2
50 100 150 200 250 300
50 100 150 200 250 300
TEMPERATURE
TEMPERATURE
1.8
1.6
HETP (mm)
1.4
1.2
1.0
.8
.6
.4
.2
1 2 3 4 5
FLOW
17
Figure 63
1ST GRAPH 2ND GRAPH
Flow Temp Flow Temp

.923 50 .923 50
.725 100 .923 100
.585 150 .923 150
.482 200 .923 200
.404 250 .923 250
.344 300 .923 300
3RD GRAPH 4TH GRAPH
Pressure Temp Pressure Temp

5 50 5 50
5 100 6.16 100
5 150 7.38 150
69
5 200 8.66 200

5 250 9.98 250
5 300 11.3 300
5TH GRAPH
HETP Flowrate
1.001 .24
0.69 .505
0.526 .77
0.456 1.03
0.476 1.53
.583 2.03
1.030 3.43
1.859 4.77
70
EPC Constant Flow Off

30 M x 0.32 mm x 0.25 uM HP5
Linear Velocity = 20.4 cm/sec 2 10&11
Constant Flow Off 9
12
Initial Pressure = 8 psi
Initial Temp 110
7
Rate 10 6
5
Final Temp 180 4 8
Final Time 7 min
FID
1 uL Column Checkout
Sample at split ratio 100:1
Area Percent Report

1 2.451 25442 20280 BV 0.020 0.1190 Pentane
2 2.830 2.09577E+07 1.27598E+07 BB 0.026 98.0245 Solvent
4 5.160 19123 10431 BB 0.029 0.0894 Undecane
5 6.504 29426 12560 BB 0.037 0.1376 4-Chlorophenol
6 7.347 30184 13787 BB 0.033 0.1412 1-Decylamine
7 8.114 35244 17470 BB 0.032 0.1648 Tridecane
9 9.647 68633 32942 BB 0.033 0.3210 Tetradecane
10 10.774 126729 33598 BB 0.062 0.5927 Acenaphthylen
11 1-Dodecanol
12 11.194 70585 29393 BB 0.038 0.3301 Pentadecane
18
Figure 64
71
EPC Constant Flow On

30 M x 0.32 mm x 0.25 uM HP5
2
Initial Pressure = 8 psi 11
Initial Temp 110
Rate 10 6
Final Temp 180 5
4 8
Final Time 7 min
FID
Sample at split ratio 100:1
Area Percent Report

1 2.455 41934 33092 BV 0.020 0.1861 Pentane
2 2.834 2.20908E+07 1.33684E+07 BV 0.026 98.0502 Solvent
4 5.089 19648 11683 BB 0.027 0.0872 Undecane
5 6.319 30584 14331 BB 0.034 0.1357 4-Chlorophenol
6 7.074 31033 16251 BB 0.029 0.1377 1-Decylamine
7 7.756 35357 20627 BB 0.027 0.1569 Tridecane
9 9.103 68292 39287 BB 0.028 0.3031 Tetradecane
10 10.018 67524 32943 BV 0.032 0.2997 Acenaphthylen
11 10.058 58702 33436 VB 0.027 0.2605 1-Dodecanol
12 10.385 69202 38486 BV 0.028 0.3072 Pentadecane
19
Figure 65
72
Important Considerations in Using EPC
• Bubble meters are ____________ obsolete.

Compare measured and calculated flows during setup and for
troubleshooting.
• EPC pressure/flow calculations apply to flow through
____________ columns.
Calibrate and evaluate conditions for work with packed
columns.
• EPC has significant advantage for the analysis of ____________
mixture and _____________ amounts.
20
Figure 66
73
Split/Splitless Inlet Design
Splitless Injection:
Inlet Design Requirements
• The majority of the injected sample is introduced into the

column.
• Higher sensitivity than the split method and therefore, used for
trace analysis.
• Peak broadening must be minimized.
21
Figure 67
74

One Bus with a Few Tourists
Canal Street
Split Vent
Bourbon Street
Column
22
Figure 68
75
Inlet Design and Operation Schematic

Purge Off
Total Septum
Flow Purge
Purge Vent
54 ml/min 53 ml/min 3 ml/min 3 ml/min
1 ml/min
ml/min Inlet Purge Flow 50 ml/min
Split Vent
Purge Control Column
Valve Head
Pressure
To Detector Head Pressure
1m
1 ml/min Gauge
l/m
in
Purge On
Total Septum
Flow Purge
Purge Vent
54 ml/min 3 ml/min Septum Purge Flow 3 ml/min
50 ml/min
Split Vent
Purge Control Column
Valve
Head
Pressure
To Detector Head Pressure

1m
Gauge
l/m
in
23
Figure 69
76
Injection Modes
Injection Modes
Split Mode
1:100 Dilution of the Column Evaluation Sample

30 M x 0.32 mm x 0.25 uM HP5
1 2
Constant Flow On
12
Initial Pressure = 12 psi at 110 degrees
9 10 11
Initial Temp 110
Rate 10 5 8
4 6
Final Temp 180 3
Final Time 7 min
Split Mode:
Split Vent Flow = 44.8
FID
Sample diluted to 1:100
Area Percent Report
1 1.574 3.98305E+07 3.85324E+07 BBAS 0.017 97.3335 Pentane
2 1.838 1069149 1209434 BV 0.015 2.6127 Solvent
3 2.074 174 229 BB 0.016 0.0004 Impurity
4 3.583 909 657 BB 0.022 0.0022 Undecane
5 4.761 1302 808 BB 0.025 0.0032 4-Chlorophenol
6 5.567 833 392 BB 0.030 0.0020 1-Decylamine
7 6.211 1683 1105 BB 0.024 0.0041 Tridecane
9 7.585 3318 2189 BB 0.024 0.0081 Tetradecane
11 8.555 2543 1695 BB 0.024 0.0062 1-Dodecanol
12 8.882 3449 2285 BB 0.024 0.0084 Pentadecane
24
Figure 70
77
Injection Modes
Splitless Mode
1:100 Dilution of the Column Evaluation Sample
30 M x 0.32 mm x 0.25 uM HP5
9
Constant Flow On
11
Initial Pressure = 12 psi at 110 degrees 10
Initial Temp 40 7
Initial Time 0 min
Rate 10 4 5 8
6
Final Temp 180
Final Time 5 min 3
Splitless Mode:
Purge On Time = 0.77 min.
FID
Area Percent Report
1 1.828 1.20696E+09 7.34754E+07 BBAS 0.199 97.7130 Pentane
2 3.443 2.78214E+07 4639343 BV 0.074 2.2524 Solvent
3 4.460 4628 2001 BV 0.035 0.0004 Impurity
4 7.807 22671 14703 BB 0.024 0.0018 Undecane
5 9.174 26020 14153 BB 0.029 0.0021 4-Chlorophenol
6 9.919 27289 12118 BB 0.032 0.0022 1-Decylamine
7 10.562 39871 28096 BB 0.023 0.0032 Tridecane
9 11.842 76661 52722 BB 0.023 0.0062 Tetradecane
10 12.599 68145 43525 BB 0.025 0.0055 Acenaphthylen
11 12.746 62741 43356 BB 0.023 0.0051 1-Dodecanol
12 13.050 80267 52718 BB 0.024 0.0065 Pentadecane
Total area = 1.2352E+09
25
Figure 71
78
Injection Modes
Splitless Injection
Solvent Effect: Initial oven temperature is maintained
below the boiling point of the solvent
causing the solvent to condense at
the head of the column "swelling" the
stationary phase and trapping the
analyte.
S
S S S
S S A S
S
S
S S
S S A S
A A S
S S S S
S A S A
S A
S S S
S S S
A = ANALYTE
S = SOLVENT
S S S
S A S S
S S S S
S A S
S A S
S A S A S S A S S
S S
S S S S S
S A S S S S S A
SOLVENT BOILING POINT INITIAL OVEN TEMP
o
o
( C) ( C)
DICHLOROMETHANE 40 10-30
CHLOROFORM 61 25-50
CARBON DISULFIDE 46 10-35
DIETHYL ETHER 35 10-25
PENTANE 36 10-25
HEXANE 69 40-60
ISO-OCTANE 99 70-90
SOLVENT AND STATIONARY PHASE MUST BE COMPATIBLE

26
Figure 72
79
Injection Modes
No Solvent Effect
30 M x 0.32 mm x 0.25 uM HP5
Constant Flow On
9 11
Initial Pressure = 12 psi at 110 degrees
Initial Temp 110
Initial Time 3 min
Rate 10 7
Final Temp 180 8
5 6
Final Time 7 min 4
Splitless Mode:
Split Vent Flow = 21 ml/min
Solvent = Pentane
FID
Area Percent Report
1 1.479 1.25642E+09 6.6195E+07 BB 0.237 99.9661 Pentane
4 3.504 19422 2160 BB 0.108 0.0018 Undecane
5 4.698 22937 2857 BB 0.108 0.0018 4-Chlorophenol
6 5.499 31525 4229 BV 0.101 0.0025 1-Decylamine
7 6.183 40959 8540 VV 0.069 0.0033 Tridecane
9 7.571 76488 24623 BB 0.046 0.0061 Tetradecane
11 8.546 63400 25018 VV 0.038 0.0050 1-Dodecanol
12 8.876 80189 34399 VB 0.036 0.0064 Pentadecane
27
Figure 73
80
Injection Modes
Demonstration of the Purge Function

Purge Off the Entire Run (No Purge On Time)
30 M x 0.32 mm x 0.25 uM HP5
Constant Flow On
4 12
5
Initial Temp 40 6
8
Rate 10
Final Temp 180
Final Time 4 min
Splitless Mode:
Solvent = Pentane
FID
Sample diluted to 1:100 Area Percent Report
1 2.014 8.44044E+08 6.36828E+07 BBAS 0.160 99.9294 Pentane
4 8.083 19245 18112 BBA 0.019 0.0023 Undecane
5 9.449 48844 21638 PV 0.033 0.0058 4-Chlorophenol
6 10.188 42947 20065 PV 0.031 0.0051 1-Decylamine
7 10.820 60389 37891 PV 0.025 0.0071 Tridecane
8 11.136 30027 19510 PV 0.025 0.0036 Methyl caprate
9 12.090 101257 66142 VV 0.024 0.0120 Tetradecane
10 12.863 93363 55617 VV 0.026 0.0111 Acenaphthylene
11 12.989 86959 54461 PV 0.025 0.0103 1-Dodecanol
12 13.291 113651 67001 PV 0.026 0.0135 Pentadecane
28
Figure 74
81
Injection Modes
Comparing Purge-On Times

Purge On 0.3 minutes
30 M x 0.32 mm x 0.25 uM HP5
1 8 11
Constant Flow On 10
6
Initial Temp 40
Initial Time 0 min
Rate 10 3 7
4 5
Final Temp 180
Final Time 4 min
Splitless Mode:
FID
1 2.081 7.90249E+08 6.14638E+07 BBAS 0.156 97.3732 Pentane
2 3.759 2.08811E+07 13516 BB 0.061 2.579 Solvent
3 8.100 19300 13516 BB 0.023 0.0024 Undecane
4 9.464 20503 11491 BB 0.028 0.0025 4-Chlorophenol
5 10.209 21299 8985 BB 0.034 0.0026 1-Decylamine
6 10.830 35759 25381 BB 0.022 0.0044 Tridecane
8 12.099 70123 48453 BB 0.023 0.0086 Tetradecane
10 12.997 56760 38181 BB 0.023 0.0070 1-Dodecanol
11 13.299 76695 49076 BB 0.025 0.0095 Pentadecane
29
Figure 75
82
Injection Modes

30 M x 0.32 mm x 0.25 uM HP5
8 11
Constant Flow On 10
Initial Temp 40 6
Initial Time 0 min
Rate 10
3 4 7
Final Temp 180 5
Final Time 4 min
Splitless Mode:
FID
1 2.038 1.15306E+09 6.32523E+07 BBAS 0.217 97.6632 Pentane
2 3.726 2.71199E+07 4285045 BV 0.079 2.2970 Solvent
3 8.097 23268 14782 BB 0.025 0.0020 Undecane
4 9.465 27011 14779 BB 0.028 0.0023 4-Chlorophenol
5 10.207 23593 10473 BB 0.033 0.0020 1-Decylamine
6 10.831 40884 28411 BB 0.023 0.0035 Tridecane
8 12.101 80177 54745 BB 0.023 0.0068 Tetradecane
10 13.000 66676 44021 PB 0.024 0.0056 1-Dodecanol
11 13.301 84329 54693 BB 0.024 0.00715 Pentadecane
30
Figure 76
83
Injection Modes

30 M x 0.32 mm x 0.25 uM HP5
Initial Temp 40 6
Initial Time 0 min
Rate 10 3 7
4 5
Final Temp 180
Final Time 4 min
Splitless Mode:
FID
1 2.025 1.07664E+09 6.34994E+07 BBAS 0.203 97.3248 Pentane
2 3.710 2.91426E+07 4250357 BB 0.087 2.6344 Solvent
3 8.093 23913 14883 BB 0.025 0.0022 Undecane
4 9.459 28871 14475 BB 0.031 0.0026 4-Chlorophenol
5 10.202 27145 11717 BB 0.033 0.0025 1-Decylamine
6 10.829 42931 30353 BB 0.022 0.0039 Tridecane
8 12.099 82470 57485 BB 0.023 0.0075 Tetradecane
10 12.997 66749 45916 PB 0.023 0.0066 1-Dodecanol
11 13.299 86018 56588 BB 0.024 0.0078 Pentadecane
31
Figure 77
84
Liners
Liners
Liners
Untreated Liners
Split/Splitless 4-mm id, 1000 ul nominal volume
Borosilica glass (untreated) with silanized glass wool plug
PN 19251-60540 Split and splitless modes, especially recommended
for rapid injections with the HP Automatic Sampler
(Univeral Liner)
Splitless 2-mm id, 250 ul nominal volume

quartz glass (untreated), open tube
PN 18740-80220 Splitless mode for slow injections
(manual and HP7671/7672 automatic samplers)
small sample volumes (< 1 ul)
and higher boiling point solvent systems
Deactivated Liners
Packed, tapered 4-mm id, 900 ul nominal volume
Borosilica glass (deactivated), silanized glass wool plug
PN 5062-3587 (deactivated)
can be self-packed
Unpacked, tapered 4-mm id,900-ul nominal volume

can be self-packed
Dual-tapered
4-mm id, 800 ul nominal volume
but preferred for splitless
32
Figure 78
85
Liners
86
Detector Parameters
Detector Parameters
Types of Detectors
Types of Detectors
GC Detector:
A Definition
A GC Detector is a device which senses the presence of a

component different from the carrier gas, and converts that
information to an electrical signal:
– Thermal Conductivity Detector (TCD)

– Flame Ionization Detector (FID)
– Electron Capture Detector (ECD)
– Nitrogen Phosphorus Detector (NPD)
– Flame Photometric Detector
– Electrolyte Conductivity Detector (ELCD, HALL)
– Photoionization Detector (PID)
– Mass Selective Detector (MSD)
– Infrared Detector (IRD)
– Atomic Emission Detector (AED)
Figure 79
88
Detector Parameters
Types of Detectors
Detectors
Types of
Detectors Brief Description
TCD Filament temperature increases as analytes present in the carrier gas pass over it, causing the
resistance to increase.
FID Components burn in a flame producing ions which are collected and converted into a current.
ECD As electronegative species pass through the detector, they capture low energy thermal electrons
causing a decrease in cell current.
NPD Nitrogen and phosphorous compounds produce increased currents in a flame enriched with
vaporized alkali metal salt.
FPD Sulphur and phosphorous compounds burn in a flame producing chemiluminescent species which
are monitored at selective wave lengths.
ELCD Halogens, sulphur, or nitrogen compounds are mixed with a reaction gas in a reaction tube. The
productsare mixed with a suitable liquid which produces a conductive solution.
PID Molecules are ionized by excitation with photons from a UV lamp. The charged particles are then
collected, producing a current.
MSD Molecules are bombarded with electrons producing ion fragments which pass into the
spectrometer's mass filter. The ions are filtered based on their mass/charge ratio.
IRD Molecules absorb infrared energy, the frequencies of which are characteristic of the bonds within
that Molecule.
AED Molecules are energized by a plasma source and separated into excited atoms. As electrons return
to their stable state, they emit light, which is element
Specific.
3
Figure 80
89
Detector Parameters
Types of Detectors
Detector Response Characteristics
Sensitivity: The response per amount of sample, that is, the slope of
the response/amount curve. The minimum amount on
the curve is defined as the minimum detectable level
(MDL).
Selectivity: A measure of which categories of compounds will give
a detector response.
Dynamic Range: The range of sample concentrations for which the

detector can provide accurate quantitation.
Figure 81
90
Detector Parameters
Types of Detectors
Comparison of GC Detectors
TCD
FID
ECD
AED
PID
IRD
N-P (N)
N-P (P)
FPD (S)
MSD
(SIM) (SCAN)
ELCD (X)
ELCD (SORN)
10 -15 10 -12 10 -9 10 -6 10 -3
fg pg ng mg mg
pptrillion ppb ppm ppthousand percent

1 ng 1 mg 1ml
1 ppm = = =
1 ml Liter Liter
Figure 82
91
Detector Parameters
Detector Sensitivity
Detector Sensitivity
Capillary Columns and Detector Selectivity
FID ECD NPD (P)
Figure 83
92
Detector Parameters
Detector Dynamic Range
Dynamic Range
Dynamic range is a measure of response vs. Quantity
Response is the signal produced by the sample.
Dynamic Range
Response increases reproducibly
Response with increased quantity.
Quantity
Linear Dynamic Range

Response Response increases proportionally
with increased quantity.
Quantity
Non-linear response, as long as it is reproducible, can

be dealt with using non-linear calibration techniques.
7
Figure 84
93
Detector Parameters
Single and Multi-Level Calibration
C
C A
C A
C A B
A B
B B
1 0.5 1.5 1.51.0 2.0 2.01.5 3.0 3.02.04.0

LEVEL 1 LEVEL 2 LEVEL 3 LEVEL 4
AREA/HEIGHT
AREA/HEIGHT
Level 4
Level 3
Level 2
Level 1
CONCENTRATION CONCENTRATION
SINGLE POINT FOR MULTI-LEVEL FOR
COMPONENT A COMPONENT C
Figure 85
94
Detector Parameters
Operating Conditions for Detectors Commonly

Used in Capillary GC Detection
Flow Rate (ml/min)
Typical Carrier + H2
Type Samples Limits Makeup Air
10-100 pg
FID Hydrocarbons 20-60 30-40 200-500
10 ppb-99%
TCD General 5-100 ng 15-30 n.a. n.a.
10 ppm-100%
ECD Organohalogens 0.05-1 pg 30-60 n.a. n.a.
Chlorinated solvents 50 ppt-1 ppm
& pesticides
Organonitrogen 0.1-10 pg
NPD 20-40 1-5 70-100
& organophosphorus 100 ppt-0.1%
compounds
FPD Sulfur compounds 10-100 pg
(393 nm) 20-40 50-70 60-80
10 ppb-100 ppm
FPD Phosphorus 1-10 pg 20-40 120-170 100-150
(526 nm) compounds 1 ppb-0.1%
PID Compounds ionized 2pg C/sec 30-40 * n.a.
by UV
ELCD 0.5 pg Cl/sec 20-40 80 n.a.
Halogens, N, S 2 pg S/sec
4 pg N/sec
FTIR Molecular vibrations 1000 pg of 3-10 n.a. n.a.
strong absorber
Tunable for any 10 pg to 10 ng
MSD (depending on 0.5-30** n.a. n.a.
species SIM vs. scan)
Tunable for any 0.1 - 20 pg/sec
AED (depending on 60-70 PRESET PRESET
element element
* Refer to Detector Manual

** Dependent upon the type of interface 9
Figure 86
95
Detector Parameters
FID
FID
FID Schematic
Flame ionization detector
designed for use with
capillary columns. FID Detector
Assembly
Air
Inlet
Capillary Column
End-Position
(1-2 mm from Top of Jet) Jet
H2 Inlet
+
Make-Up
Flame ionization
detector gas controls
FID OFF PRESS
AIR FID IGNITOR

OFF OFF
HYDROGEN AUX GAS Exit End of Column
10
Figure 87
96
Detector Parameters
FID
Compounds with Little or No FID Response

Rare gases NH CS 2
3
Nitrogen oxides H2 COS
Silicon halides CO O2
HO CO N
2 2 2
Perhalogenated cpds HCOH HCOOH
Overcoming FID Selectivity
Problem: CO and CO trace analysis

2
(best TCD sensitivity 20-50 ppm)
CO Nickel 350
Good
OR + H2 Catalyst tube CH4
Solution: CO2
Sensitivity as good as 0.1 ppm
11
Figure 88
97
Detector Parameters
TCD
TCD
Single Filament TCD

EXIT
COLUMN flow enters the center
of three ports.
AUXILIARY, or make-up, flow DETECTOR

"sheathes" the column
CELL
minimizing diffusion at
the end of the column.
3.5 mL
FILAMENT VOLUME
REFERENCE flow is
directed to either
one of the outside
ports into the detector
cell. The entry port is
determined by the SWITCHING
SOLENOID, REFERENCE
AUXILIARY
REFERENCE
COLUMN
SWITCHING
SOLENOID
REFERENCE
REFERENCE FLOW = 1.5 x ( COLUMN + AUXILIARY ) FLOW
TCD OFF
AUX GAS
OFF Thermal conductivity
REF
detector gas controls
12
Figure 89
98
Detector Parameters
TCD
Type of Carrier Gas
Thermal Conductivity Relative to Helium

Relative Thermal
Compound Conductivity
Carbon Tetrachloride 0.05
Benzene 0.11
Hexane 0.12
Argon 0.12
Methanol 0.13
Nitrogen 0.17
Helium 1.00
Hydrogen 1.28
13
Figure 90
99
Detector Parameters
FID and TCD Comparison
Comparison of FID and TCD Analysis

FID Analysis

30 M x 0.32 mm x 0.25 uM HP5
1
Initial Pressure = 12 psi 11
Initial Temp 110
Initial Time 3 min 6 7
Rate 10 5
Final Temp 180 4
8
Final Time 7 min 3
FID
Sample
Area Percent Report

1 1.591 127589 181613 BV 0.012 0.1952 Pentane
2 2.083 6.40112E+07 4.70123E+07 BV 0.023 97.9545 Solvent
3 2.083 20660 23683 BV 0.018 0.0316 Impurity
4 3.599 56809 41836 BB 0.022 0.0869 Undecane
5 4.482 81723 50109 BB 0.026 0.1251 4-Chlorophenol
6 5.526 96577 61596 BB 0.024 0.1478 1-Decylamine
7 6.233 103810 66682 BB 0.025 0.1589 Tridecane
9 7.614 203872 122264 BB 0.026 0.3120 Tetradecane
11 8.586 174116 105709 BB 0.025 0.2664 1-Dodecanol
12 8.913 217376 127896 BB 0.025 0.3326 Pentadecane
14
Figure 91
100
Detector Parameters

TCD Analysis: Low Sensitivity

30 M x 0.32 mm x 0.25 uM HP5
Initial Pressure = 12 psi
Initial Temp 110
Initial Time 3 min 8 10 11
Rate 10 9
Final Temp 180 4 5 6
Final Time 7 min 3 7
TCD, low sensitivity

Sample
Area Percent Report

1 1.477 122 197 BV 0.010 0.1535 Pentane
2 1.709 78595 64677 BV 0.020 98.7155 Solvent
3 3.359 47 32 BB 0.024 0.0591 Undecane
4 4.532 89 54 BB 0.027 0.1112 4-Chlorophenol
5 5.275 78 52 BB 0.024 0.0985 1-Decylamine
6 5.989 83 49 BB 0.026 0.1037 Tridecane
8 7.381 150 87 BB 0.026 0.1886 Tetradecane
10 8.360 145 83 BB 0.026 0.1815 1-Dodecanol
11 8.691 153 87 BB 0.028 0.1922 Pentadecane
Total area = 79617
15
Figure 92
101
Detector Parameters

TCD Analysis: High Sensitivity

30 M x 0.32 mm x 0.25 uM HP5
Initial Pressure = 12 psi 8 11
10
Initial Temp 110
9
Initial Time 3 min 4 5 6
Rate 10
Final Temp 180 3 7
Final Time 7 min
TCD, high sensitivity

Sample
Area Percent Report

1 1.477 3498 5319 BV 0.011 0.6309 Pentane
2 1.709 526404 292634 BBAS 0.022 94.9492 Solvent
3 3.361 1269 903 BB 0.022 0.2290 Undecane
4 4.535 2458 1457 BB 0.026 0.4433 4-Chlorophenol
5 5.279 2264 1420 BB 0.025 0.4083 1-Decylamine
6 5.991 2135 1349 BB 0.025 0.3850 Tridecane
8 7.383 4037 2450 BB 0.026 0.7281 Tetradecane
10 8.361 3882 2299 BB 0.027 0.7003 1-Dodecanol
11 8.692 4218 2415 BB 0.027 0.7609 Pentadecane
Total area = 554406
16
Figure 93
102
Detector Parameters
ECD
ECD
Electron Capture Detector Schematic
Anode Purge
Vent
Anode
Plated Ni
Surface
Nickel Plating
Fused Silica
Liner
Makeup Gas Makeup Gas

Adapter
Column
Trace Analysis
Halogenated compounds
Nitro group compounds
Conjugated double bond compound
Common Applications
Environmental (organo chlorine pesticides)
17
Figure 94
103
Detector Parameters
NPD
NPD
Nitrogen Phosphorus Detector Schematic
NPD
Collector
Air
Inlet
Active
Capillary Column Element
End-Position
(1-2 mm from Top of Jet) Jet
H2 Inlet
+
Make-Up
* Active element is a potassium or rubidium alkali metal salt.
Diagram of a nitrogen phosphorous detector designed for

optimal performance with capillary columns.
18
Figure 95
104
Detector Parameters
NPD
Type of Column
Carrier Conditions
Oven Conditions
Detector Parameters
Sample Information
19
Figure 96
105
Detector Parameters
NPD
106
Exercise 1: Determining Efficiency
Part I: 30 M x 0.53mm x 0.88um HP1 Column
1 2
8
5 9
4 11
3 6
10
Column head pressure: 3 psi

Isothermal 160 degrees FID
1 uL Column Checkout sample
Pk# Ret Time Peak Width Name
1 1.477 0.015 Pentane
2 1.609 0.021 Solvent
3 2.333 0.022 Undecane
4 2.638 0.029 4-Chlorophenol
5 3.143 0.033 1-Decylamine
6 3.681 0.036 Tridecane
7 3.738 0.035 Methyl Caprate
8 4.970 0.051 Tetradecane
9 5.823 0.062 Acenaphthylene
10 6.009 0.063 1-Dodecanol
11 6.982 0.074 Pentadecane
108
1) Calculate the Linear Velocity, Flowrate, HETP, and Plates/Meter using peak
8 and use peak 1 as the non-retained species.
2) Using the results from your previous calculations, complete the following
table:
30 M x 0.53 x 0.88 HP1

Column Head Linear
Pressure Velocity Flowrate
(psi) (cm/sec) (mL/min) HETP Plates/Meter
1 10.7 1.4 1.75 571
2 20 2.7 1.2 808
3
4 44 5.9 1.3 768
7 78 10.3 2.0 506
11 121 16 3.53 283
20 213 28 8.4 119
109
3) Use the graph below and plot the HETP vs. linear velocity for each of the
columns. Construct on graph paper:
4
3.5
2.5
1.5
0.5
0 20 40 60 80 100 120 140
110
Part II: 30 M x 0.32mm x 0.25um HP 5 Column
1 2 8
5
3 4 6
9 11
10
4) Use the data below to plot HETP vs. LV for this column:
Make the plot on the same graph for comparison:
Column Head
Pressure Linear Flowrate
(psi) Velocity (mL/min) HETP Plates/Meter
2 5.04 0.24 1.001 999
4 10.5 0.505 0.69 1443
6 15.9 0.77 0.526 1900
8 21.3 1.03 0.456 2195
12 31.8 1.53 0.476 2103
16 42 2.03 0.583 1715
28 71.1 3.43 1.030 971
40 99 4.77 1.859 538
111
5) Which column is more efficient?
112
Exercise 2: Comparing Column
Diameter and Resolution
Exercise 2: Comparing Column Diameter and Resolution
Worksheet
Worksheet
Using the following equation for determining resolution quantitatively, compare
three columns by calculating the "R" value for the separation of C-14 and
acenaphthlalene using the data on the next three pages:
RT1 = retention time of the first of the two

R = 1.18 (RT2) – RT1) peaks that one is calculating the
----------------------- resolution of
(W1 + W2)
RT2 = retention time of the second peak
W1 = peak width of first peak
W2 = peak width of second peak
Packed column R = _______________
0.53 column R = _______________
0.32 column R = _______________
Which column diameter yielded the best “R” value?
114
Packed Column Analysis: 6' x 1/8" 5 % OV101 on 80/100
Chromosorb
Packed Column Analysis: 6' x 1/8" 5 % OV101 on

80/100 Chromosorb
1 2 4
7
6 9
5
11&12
8 10
Packed Column Analysis: 6' x 1/8" 5 % OV101 on 80/100 Chromosorb

Column Flowrate = 30 mL/min. Linear Velocity = 12.4 cm/sec
1 uL HP Column Checkout Sample
Area Percent Report
PK # Ret Time Area Height Type Width Area % Name
1 0.246 2879398 4458532 BV 0.015 0.2317 Pentane
2 0.341 1.22622E+009 8.10852E+008 HB S 0.026 98.6695 Solvent
4 1.006 823259 279443 BB T 0.046 0.0662 Undecane
5 1.361 916089 177078 BB T 0.073 0.0737 4-Chlorophenol
6 2.512 1387522 196260 BV 0.106 0.1116 1-Decylamine
8 2.630 749162 97326 VB 0.113 0.0603 Methyl Caprate
7 4.120 2650317 232666 BV 0.177 0.2133 Tridecane
9 4.505 2331063 193209 VB 0.187 0.1876 Tetradecane
11 & 6.830 2807565 146329 VB 0.297 0.2259 1-Dodecanol
12 and
Pentadecane
115
Capillary Column Analysis: 30 M x 0.53 mm x 0.88 HP1
Capillary Column Analysis: 30 M x 0.53 mm x

0.88 HP1
1 2
9
12
7&8 11
10
6
4 5
Capillary Column Analysis: 30 M x 0.53 mm x 0.88 HP1

Column Flowrate = 2.6 mL/min Linear Velocity = 19.7 cm/sec
1 uL HP Column Checkout Sample at Split Ratio = 39.1
Area Percent Report

1 2.541 333138 156491 BV 0.033 0.7688 Pentane
2 2.711 4.24499E+007 1.81871+007 PV 0.036 97.9577 Solvent
4 3.438 27293 11612 BB 0.0630 0.0630 Undecane
5 3.743 44075 13854 BB 0.1017 0.1017 4-Chlorophenol
6 4.206 38866 12775 BB 0.0897 0.0897 1-Decylamine
7&8 4.670 71919 16254 BB 0.1660 0.1660 Tridecane
9 5.772 96872 25091 BB 0.2235 0.2235 Tetradecane
11 6.808 91419 16880 VB 0.2110 0.2110 1-Dodecanol
12 7.420 102251 20686 BB 0.2360 0.2360 Pentadecane
116
Capillary Column Analysis: 30 M x 0.32 mm x 0.25 uM HP5
Capillary Column Analysis: 30 M x 0.32 mm x 0.25

uM HP5
1 2 6 7 9
10 11 12
4 5
3
8

Column Flowrate = 1 mL/min Linear Velocity = 20.5 cm/sec
1 uL HP Column Checkout Sample at Split Ratio = 100:1
Area Percent Report
1 2.442 62321 45133 BV 0.022 0.2127 Pentane
2 2.556 2.90451E+007 1.87002E+007 VV 0.024 99.1066 Solvent
3 2.672 8303 5036 VB 0.026 0.0283
4 3.100 10129 7143 BB 0.023 0.0346 Undecane
5 3.511 14978 7438 BB 0.032 0.0511 4-Chlorophenol
6 3.816 16871 9417 BB 0.028 0.0576 1-Decylamine
7 4.156 17124 9425 BB 0.029 0.0584 Tridecane
9 5.179 33486 14578 BB 0.036 0.1143 Tetradecane
11 6.542 29540 8682 BB 0.053 0.1008 1-Dodecanol
12 6.789 34293 11407 BB 0.047 0.1170 Pentadecane
117
118
Exercise 3: Comparing Column Length
and Resolution
Exercise 3: Comparing Column Length and Resolution
Worksheet
Worksheet
three columns by calculating the "R" value for the separation of C-14 and
acenaphthlalene using the data from the next three pages:

R = 1.18 (RT2) – RT1) peaks that one is calculating the
----------------------- resolution of
(W1 + W2)
RT2 = retention time of the second peak
10 meter column R = _______________
20 meter column R = _______________
30 meter column R = _______________
Was there an effect on the retention times of the components?
________________________________________________________________
Did doubling the length, double the resolution?
________________________________________________________________
Using the Bourbon Street Analogy, how would we explain the phenomenon of
increasing column lengths?
________________________________________________________________
________________________________________________________________
120
Worksheet
Did the 10 meter column separate all of the peaks?
________________________________________________________________
121
Capillary Analysis: 10 M x 0.53 mm x 0.88 uM HP1
1
2 6
5 9
10
4 7&8 11 12

Area Percent Report
1 0.527 231973 506649 BV 0.011 0.4622 Pentane
2 0.582 4.91296E+007 4.85842E+007 HBAS 0.018 97.8832 Solvent
4 0.932 39379 45292 BV 0.014 0.0785 Undecane
5 1.080 61167 58218 BB 0.017 0.1219 4-Chlorophenol
6 1.334 78767 59735 BB 0.021 0.1569 1-Decylamine
7&8 1.617 104643 43750 BB 0.034 0.2085 Tridecane
9 2.294 140234 57536 BB 0.038 0.2794 Tetradecane
11 2.844 123994 41236 BB 0.048 0.2470 1-Dodecanol
12 3.376 148918 39432 BB 0.059 0.2967 Pentadecane
122
1
2
9
5 6 10
4 7
11 12

Area Percent Report
1 1.005 93377 151911 BV 0.010 0.888 Pentane
2 1.112 1.04351E+008 7.90804E+007 BBAS 0.021 99.2401 Solvent
4 1.768 37032 31069 BV 0.019 00352 Undecane
5 2.056 54979 36934 BB 0.024 0.0523 4-Chlorophenol
6 2.556 15379 7446 BB 0.031 0.0146 1-Decylamine
7 3.063 66376 29476 BV 0.035 0.0631 Tridecane
8 3.126 31186 14012 VB 0.035 0.0297 Methy caprate
9 4.343 129261 38695 BB 0.052 0.1229 Tetradecane
11 5.401 111190 26843 BB 0.065 0.1057 1-Dodecanol
12 6.391 135985 25968 BB 0.082 0.1293 Pentadecane
123
Capillary Column Analysis: 30 M x 0.53 mm x 0.88

uM HP1
1
2
9
5 6
4 7 10
11 12

Area Percent Report
1 1.460 115928 132851 BBA 0.014 0.1455 Pentane
2 1.620 7.90305E+007 5.3877E+007 HBAS 0.022 99.2190 Solvent
4 2.573 25248 16312 BB 0.024 0.0317 Undecane
5 2.984 37198 17834 BB 0.033 0.0467 4-Chlorophenol
6 3.682 45920 18003 BB 0.039 0.0577 1-Decylamine
7 4.459 44286 15239 BV 0.045 0.0556 Tridecane
8 4.54. 21118 7177 VB 0.046 0.0265 Methy caprate
9 6.325 85934 20143 BB 0.067 0.1079 Tetradecane
11 7.839 71163 13334 BB 0.083 0.0893 1-Dodecanol
12 9.310 89398 13576 BB 0.103 0.1122 Pentadecane
124
Exercise 4: Comparing Column Film
Thickness and Resolution
Exercise 4: Comparing Column Film Thickness and Resolution
Worksheet
Worksheet

two columns by calculating the "R" value for the separation of C-14 and
acenaphthlalene using the data shown on the next two pages:

peaks that one is calculating the
R = 1.18 (RT2) – RT1) resolution of
----------------------- RT2 = retention time of the second peak
(W1 + W2)
0.88 uM film column R = _______________
2.65 uM film column R = _______________
Was there an effect on the retention times of the components?
________________________________________________________________
Did tripling the film thickness triple the resolution?
________________________________________________________________
Using the Bourbon Street Analogy, how would we explain the phenonmenon of
increasing column film thickness?
________________________________________________________________
________________________________________________________________
126
Worksheet
________________________________________________________________
Did the columns separate all of the peaks?
________________________________________________________________
127
1
2 6 9
5 10
7&8
4 11 12
Column Flowrate = 1 mL/min Linear Velocity = 48 cm/sec

Area Percent Report
1 0.347 121201 360718 BV 0.006 0.2766 Pentane
2 0.382 4.25931E+007 4.41108E+007 HBAS 0.017 97.2182 Solvent
4 0.615 55319 76048 BV 0.012 0.1263 Undecane
5 0.713 76636 94349 BV 0.014 0.1749 4-Chlorophenol
6 0.882 100878 93840 BV 0.017 0.2303 1-Decylamine
7&8 1.069 145694 78145 BB 0.030 0.3325 Tridecane
9 1.515 190617 100550 BB 0.030 0.4351 Tetradecane
11 1.878 161632 70438 PV 0.036 0.3689 1-Dodecanol
12 2.229 200301 68188 BB 0.046 0.4572 Pentadecane
128
1 2
5
6
9 10
4
7&8 11
12
Column Flowrate = 1 mL/min Linear Velocity = 40 cm/sec

Area Percent Report
1 0.418 164606 376839 BV 0.007 0.3347 Pentane
2 0.542 4.81769E+007 3.22537E+007 BBA 0.026 97.9559 Solvent
4 1.297 41141 23557 BB 0.028 0.0837 Undecane
5 1.617 62624 32634 BB 0.030 0.1273 4-Chlorophenol
6 2.168 79198 27992 BB 0.044 0.1610 1-Decylamine
7&8 2.788 106786 19792 BB 0.077 0.2171 Tridecane
9 4.261 141902 25125 BB 0.089 0.2885 Tetradecane
11 5.456 124564 17972 BB 0.109 0.2566 1-Dodecanol
12 6.618 148478 16669 BB 0.139 0.3019 Pentadecane
129
130
Exercise 5: Calculating the Split Ratio
Worksheet
Worksheet
Using data from the chromatograms on the following pages and the given
formulas,complete the table below:
Column Flowrate (mL/min) = π r2 ū 60

R = Column radius in cm.
ū = Average linear velocity in cm./sec.
col length (cm.)

ū = -----------------------------------------------
R.T. (sec) of non-retained species
Split Vent Flowrate + Column Flowrate

Split Ratio = -------------------------------------------------------
Column Flowrate
Split Vent Column Split Area Count

Flow Flowrate Ratio of C-14
44.8
101.7
220
132
Split Vent Flow = 44.8 mL/min

Capillary Column Analysis: 30 M x 0.32 mm x 0.25 uM HP 5
12
1
2 9
11
10
7
6
5
4
8
3
Column Head Pressure: 12 psi

Temperature Program: Init. Temp: 110 Initial Time: 3 min . Rate: 10
Final Temp: 180 Final Temp: 7 min.
FID: 1 uL of Column Checkout Sample
Area Percent Report
1 1.591 127589 181613 BV 0.012 0.1952 Pentane
2 1.844 6.40112E+007 4.70123E+007 BV 0.023 97.9545 Solvent
3 2.083 20660 23683 BV 0.018 0.0316 Impurity
4 3.599 56809 41836 BB 0.022 0.0869 Undecane
5 4.782 81723 50109 BB 0.026 0.1251 4-Chlorophenol
6 5.526 96577 61596 BB 0.024 0.1478 1-Decylamine
7 6.233 103810 66682 BB 0.025 0.1589 Tridecane
9 7.614 203872 122264 BB 0.026 0.3120 Tetradecane
11 8.586 174116 10509 BB 0.025 0.2664 1-Dodecanol
12 8.913 217376 127896 BB 0.025 0.3326 Pentadecane
133

1
2 9 12
11
10
7
5 6
4
8
3

Temperature Program: Init. Temp: 110 Initial Time: 3 min Rate: 10
Final Temp: 180 Final Time: 7 min
Area Percent Report
1 1.593 83755 121735 BV 0.011 0.2454 Pentane
2 1.846 3.35316E+007 3.21424E+007 BV 0.017 98.2293 Solvent
3 2.087 6187 8569 BV 0.016 0.0181 Impurity
4 3.614 25332 18560 BB 0.022 0.0742 Undecane
5 4.800 37070 23577 BB 0.025 0.1086 4-Chlorophenol
6 5.553 40633 24559 BB 0.025 0.1190 1-Decylamine
7 6.254 45626 29838 BB 0.024 0.1337 Tridecane
9 7.631 88830 57276 BB 0.024 0.2602 Tetradecane
11 8.601 76148 49580 BB 0.024 0.2231 1-Dodecanol
12 8.928 93985 59704 BB 0.025 0.2753 Pentadecane
134
Split Vent Flow = 220 mL/min

1
2 11
9
12
10
7
5 6
4 8
3

Temperature Program: Init. Temp: 110 Initial Time: 3 min Rate: 10
Final Temp: 180 Final Time: 7 min
Area Percent Report
1 1.599 31703 46779 BV 0.011 0.1763 Pentane
2 1.852 1.77427E+007 1.94882E+007 BV 0.026 0.026 Solvent
3 2.093 2856 3951 BV 0.016 0.0159 Impurity
4 3.619 10121 7515 BB 0.021 0.0563 Undecane
5 4.800 16549 10729 BB 0.024 0.0920 4-Chlorophenol
6 5.560 15419 8910 BB 0.026 0.0858 1-Decylamine
7 6.251 17464 11681 BB 0.024 0.0971 Tridecane
9 7.623 33334 21782 BB 0.024 0.1854 Tetradecane
11 8.591 29029 19256 BB 0.024 0.1615 1-Dodecanol
12 8.918 34741 22514 BB 0.024 0.1932 Pentadecane
135
136
Exercise 6: Split and Splitless Injection
Worksheet
Worksheet
6) How could you improve the sensitivity, assuming that the Integration
parameters have been set for maximum sensitivity?
7) You want to decrease the analysis runtime while maintaining the separation
of components 1 and 2. Comment on the validity of each of the following
approaches.
a. Increase the initial temperature.
b. Shorten the column to 25 m.
138
Worksheet
c. Decrease the “purge on” time.
d. Use a solvent with a higher boiling point.
8) How would you improve the baseline and reduce the solvent tailing for the
following:
139
Worksheet
140
Appendix
Appendix
References
References
References
• High Resolution Gas Chromatography

Third Edition, K.J. Hyver, Editor
Hewlett-Packard 1989 PN 5950-3562
• GC Inlets – An Introduction
Mathew Klee
• Detectors for Gas Chromatography – A Practical Primer
Rosemary Buffington, Mike Wilson
Hewlett Packard 1987 PN 5958-9433
• Electronic Pressure Control in Gas Chromatography
Sally Stafford
142
Appendix
Application Notes
Application Notes
Application Notes
Sorted by Industry:
Fuels 1
Chemicals/Polymers 4
Pharmaceutical 5
Toxicology/Forensics 6
Environmental 7
Foods/Favor 8
Bioscience 10
Figure 97
143
Appendix
Application Notes
Application Notes
144
Appendix
Application Notes
Application Notes
145
Appendix
Application Notes
Application Notes
146
Appendix
Application Notes
Application Notes
147
Appendix
Application Notes
Application Notes
148
Appendix
Application Notes
Application Notes
149
Appendix
Application Notes
Application Notes
10
150
Appendix
Application Notes
Application Notes
11
151
Appendix
Application Notes
Application Notes
12
152
Appendix
Application Notes
Application Notes
13
153
Appendix
Bibliography
Bibliography
Bibliography
14
154
Appendix
Bibliography
Bibliography
15
155
Appendix
Bibliography
Bibliography
16
156
Appendix
Bibliography
Bibliography
17
157
Appendix
Bibliography
Bibliography
18
158
Appendix
Bibliography
Bibliography
19
159
Appendix
Bibliography
Bibliography
20
160
Appendix
Exercise Answers
Exercise Answers
Exercise 1 - Determining Efficiency
col length (cm)

A. Linear velocity, u = --------------------------------------------
R.T.(ser) of non-retained species
3000 cm
u = ------------------------------ = 33.8 cm/sec
1.477 min x 60 sec/,in
Flow Rate = π r 2 u 60 d=
0.53m
=
0.053cm
= (3.14) (0.0265 cm) 2 (33.8 cm) (60 sec)
r = 0.0265cm
----------- ---------
sec min
= 4.47 ml/min
L (mm) t R1
HETP = ------------ n = 5.545 ( --------------) 2
n wh
30,000 4.970 - 1.477

= ----------- n = 5.545 ( -------------------) 2
26,011 0.051
= 1.15 n = 26,011
n 26,011
Plates/meter = ------ = -----------
L 30
= 867
B. 33.8 , 4.47 , 1.15 , 867
161
Appendix
Exercise Answers
C.
4
•
3.5
0.53 Column
2.5
•
2 Part D
•
1.5
• 0.32 Column
•
•
•
1
•
•
• •
0.5
• •
0 20 40 60 80 100 120 140

E. The 0.32 column is more efficient since it has a lower HETP
minimum.
162
Appendix
Exercise Answers
Exercise 2 - Comparing Column Diameter and

Resolution
1.18 (RT2 - RT1)

R= ---------------------------
(W1 + W2)
1.18 (5.678 - 4.505)

Packed Column: R = -----------------------------
(0.187 + 0.253)
1.18 (1.173)
R = -------------------- = 3.15
0.44
1.18 (6.659 - 5.772)

0.53 Column: R = -----------------------------
(0.2235 + 0.1828)
1.18 (0.887)
R = -------------------- = 2.58
0.4063
1.18 (6.315 - 5.179)

0.32 Column: R = -----------------------------
(0.036 + 0.046)
1.18 (1.136)
R = -------------------- = 16.3
0.082
163
Appendix
Exercise Answers
Exercise 3 - Comparing Column Length and Resolution
1.18 (RT2 - RT1)

R= ---------------------------
(W1 + W2)
1.18 (2.652 - 2.294)

10 Meter Column: R = -----------------------------
(0.038 + 0.042)
1.18 (0.358)
R = -------------------- = 5.28
0.08
1.18 (5.018 - 4.343)

20 Meter Column: R = -----------------------------
(0.052 + 0.057)
1.18 (0.675)
R = -------------------- = 7.31
0.109
1.18 (7.308 - 6.325)

30 Meter Column: R = -----------------------------
(0.036 + 0.046)
1.18 (.983)
R = ----------------------------- = 7.94
0.146
164
Appendix
Exercise Answers
Exercise 4 - Comparing Film Thickness and Resolution
1.18 (RT2 - RT1)

R= ---------------------------
(W1 + W2)
1.18 (1.751 - 1.515)

0.88 uM Film: R = -----------------------------
(0.03 + 0.03)
1.18 (0.236)
R = -------------------- = 4.64
0.06
1.18 (5.036 - 4.261)

2.65 uM Film: R = -----------------------------
(0.089 + 0.090)
1.18 (0.775)
R = -------------------- = 5.11
0.179
165
Appendix
Exercise Answers
Exercise 5 - Calculating the Split Ratio
Col Flow = π r2 u 60 (3000) (60)

2
= (3.14) (0.032/2) -------------------
(1.591) (60)
= 1.52 mL/min
44.8 + 1.52
Split Ratio = ------------------ = 30.5
1.52
Area Count = 203,872
(3000)
Col Flow = (3.14) (0.016) 2 ------------ = 1.52 mL/min
1.593
= 1.52 mL/min
101.7 + 1.52
Slit Ratio = ------------------ = 67.9
1.52
Area Count = 88,830
Split Vent Flow = 220
(3000)
2
Col Flow = (3.14) (0.016) ------------ = 1.51 mL/min
1.599
= 1.52 mL/min
220 + 1.51
Split Ratio = ------------------ = 146.7
1.51
Area Count = 33,334
166
Appendix
Exercise Answers
Exercise 6 - Split Injection and Splitless Injection
1. Decrease the split ratio. Use a more sensitive detector.
2. A. A good approach if the higher temp will still allow

solvent focusing.
B. May cause the peaks of interest to merge.
C. Decreasing the purge on time may result in loss of
sample and thus, loss of sensitivity.
D. Would allow starting at a higher initial oven temperature.
Probably the best approach.
3. Perhaps hold the purge off longer or increase the purge on

time.
Perhaps use a solvent with a lower boiling point so that a
lower initial oven temp could be used.
167
Appendix
Exercise Answers
168

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Introduction to

Capillary Gas Chromatography

Manual Part Number H2615-90000

Agilent Technologies, Inc

 2000 by Agilent Technologies, Inc.

In This Section, You Will Learn:

• Introduction: • Sample Introduction

Typical Gas Chromatograph

What is Capillary Gas Chromatography

Capillary Column Analysis:

Area Percent Report

Typical Chromatograph from the 3396 Integrator

RUN# 54 JAN 3, 1901 00:56:26

SAMPLE NAME: BGC SAMPLE# 1

RT AREA TYPE WIDTH AREA%

What Must Be Done in Order to Perform a GC

What will Be Discussed in This Course

Identification of what must be done; Not how to perform

• Topics NOT Included:

Sample Preparation Considerations

Capillary Columns Require CLEAN SAMPLES!

• ____________ ("Dilute and Shoot")

• Have as ____________ a Sample as Possible.

Column Selection Techniques

– Tray a column that is handy.

What are the Column Types?

Porous Layer 30 Meter X 0.53 mm X 0.88um HP1

Length Diameter Film Type

6 Feet X 1/8 inch 5% OV101 on 80/100 Chromosorb

Length Diameter Concentration Type of

Capillary Column Analysis: 1 2

Area Percent Report

Capillary Column – 0.53mm ID

Capillary Column Analysis:

Area Percent Report

Capillary Column – 0.32mm ID

Capillary Column Analysis:

Area Percent Report

What Does the Column Provide?

____________ is a measure of the ability of a column to separate into two

Let’s look at how the separation D

A Trip Down Bourbon Street

Non-Drinker: 1 Bar in 1 minutes

Bourbon Street with 4 Bars

Time for Non-Drinker to Elute at End of Street: ____ minutes.

Joe's Place Howard's Two Guys Sam's Spirits

Time for Bourbon Drinker to Elute at End of Street: ____ minutes.

Joe's Place Howard's Two Guys Sam's Spirits

Time for Hurricane Drinker to Elute at End of Street: ____ minutes.

Non-Drinker Bourbon Drinker Hurricane Drinker

Basic Resolution Equation

Flowrate / Linear Velocity Film Thickness Type of Stationary Phase

Basic Resolution Equation (cont.)

Flowrate / Linear Velocity Film Thickness Type of Stationary Phase

Flow Rate/Linear Velocity and Resolution

Chromatograms Using Different Flow

Capillary Column Analysis:

Pk# Ret. Time Name

Chromatograms Using Different Flow

Capillary Column Analysis:

Pk# Ret. Time Name

Chromatograms Using Different Flow

Capillary Column Analysis:

Pk# Ret. Time Name