Jack Greer

1101, N State St, Bertelsmeyer Hall

Rolla, MO-65409

16th November 2017

ATTN: Dr. Ali Rownaghi

1101, N State St, Bertelsmeyer Hall

Rolla, MO-65409

RE: Composition Lab - Report #05

Dear Dr. Rownaghi:

This report was written to fulfill the fifth of six lab reports assigned in the Chemical Engineering 4100
course. This report, Composition, was developed and compiled by course Group 10 within one week of
performance of the composition lab.

The purpose of the composition lab report is to better understand key concepts of composition analysis by
developing a calibration curve for the Agilent 7890 Gas Chromatograph. After accounting for error and
careful analysis, Group 10 has determined calibration curves for each component in the gas
chromatograph:

● The methyl alcohol calibration function is y=0.0154x+0.0741

● The isopropyl alcohol calibration function is y=0.0083x+0.1244
● The n-butyl alcohol calibration function is y=0.0052x+0.0263
As well as determined the actual composition of the unknown solution C
● 0.283388567 % mass methyl alcohol
● 0.439519183 % mass isopropyl alcohol
● 0.278205767 % mass n-butyl alcohol
The members of Group 10 have benefitted greatly from both the content learned from this lab and the
instruction from the various Teaching Assistants of this course. Thank you to all in advance for reviewing
and giving feedback of this report.

Sincerely,

Jack Greer

COMPOSITION
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A TECHNICAL REPORT

by

Maxwell Hopkins, Jack Greer, Mason Carey, Yaw Abeasi

Presented to Dr. Ali Rownaghi of the Department

CHEMICAL AND BIOCHEMICAL ENGINEERING

In Partial Fulfillment of the Requirements for the Course

Chemical Engineering Lab 4100

in

CHEMICAL ENGINEERING

11/16/2017
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Executive Summary

The composition lab focused on developing technical lab skills and use of lab machinery.
The lab also served to further develop a sense for data analysis by examining and developing
understandable results from a gas chromatograph/mass spectrometer. The lab required each
technician to prepare six samples for testing; five samples whose compositions were known, and
one sample whose composition was unknown, culminating in a total of 24 individual samples.
These samples, once prepared, were loaded into the Agilent 7890 Gas Chromatograph and
analyzed. Using the values of the known sample compositions, the mass percents of each methyl
alcohol, n-butyl alcohol, and i-propyl alcohol were determined from the given values of solutions
A and B. These mass percentages were then compared to the percent area from the graphs out of
the Agilent 7890. The data was then fit to a linear trendline and the general equation of those
trend lines were used as independent models for each component. These models were then used
to develop a percentage for each component in solution C. These trend lines and composition
percents are as follows:
● The methyl alcohol calibration function is y=0.0154x+0.0741
● The isopropyl alcohol calibration function is y=0.0083x+0.1244
● The n-butyl alcohol calibration function is y=0.0052x+0.0263
Composition of solution C is:
● 0.283388567 % mass methyl alcohol
● 0.439519183 % mass isopropyl alcohol
● 0.278205767 % mass n-butyl alcohol

Objectives

● Calibrate the Agilent 7890 Gas Chromatograph for methyl alcohol, n-butyl alcohol, and i-
propyl alcohol.

Background

The Gas Chromatography/Mass Spectrometry (GC/MS) instrument separates chemical

mixtures (the GC component) and identifies the components at a molecular level (the MS
component. It is one of the most accurate tools for analyzing unknown mixtures (samples) in the
chemical industry. The GC/MS is composed of two main building blocks; these are the Gas
Chromatograph and Mass Spectrometer. The gas chromatograph utilizes a capillary column
which depends on the column's dimensions (length, diameter, film thickness) as well as the
phase properties. The GC consist of two phases called the stationary and mobile phases. The
mobile phase is comprised of the carrier gas and an inert gas such as helium, argon or nitrogen.
The stationary phase consists of a packed column in which the packing or solid support itself acts
as stationary phase, or is coated with the liquid stationary phase (=high boiling polymer). Most
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analytical gas chromatographs use capillary columns, where the stationary phase coats the walls
of a small-diameter tube directly (i.e., 0.25 μm film in a 0.32 mm tube)
The separation of the compounds in the mixture are based on the different strength of interaction
of the compound with the stationary phase. The stronger the interaction is, the longer the
compound takes to interact with the stationary state; which in turn causes the compound to
migrate through the column at a slower pace thus increasing the time taken. There are five main
factors that affect the separation of compounds in a mixture.
1. Vapor Pressure: The boiling point of a compound is usually related to its polarity. The
lower the boiling point, the higher the vapor pressure of the compound and a shorter
retention time
2. Polarity of components versus Polarity of stationary phase in column: If polarity of the
stationary phase and compound is similar, the retention time will increase due to strong
interaction between the compound and the stationary phase. As a result polar compounds
have longer retention time with polar stationary phases but has shorter times in non polar.
3. Column Temperature: A very high column temperature results in a very short retention
time.
4. Flow rate of Carrier Gas: For high flow rates the retention time is reduced because the
components or compounds have little time to interact with stationary phase.
5. Column length: A longer column generally improves separation. The retention time
increases proportionally to the length of the column.

The main or primary goal of the Mass Spectrometer is to quantify the amount of substance. This
is done by comparing relative concentration among the atomic masses in the generated spectrum.
There are two types of analysis; comparative and original. Comparative is where the spectrum
produced is compared to other spectra to determine the component or compound. Another
method of analysis measures the peaks in relation to one another. In this method, the tallest peak
is assigned 100% of the value, and the other peaks being assigned proportionate values. All
values above 3% are assigned. The total mass of the unknown compound is normally indicated
by the parent peak. The value of this parent peak can be used to fit with a chemical formula
containing the various elements which are believed to be in the compound. The isotope pattern in
the spectrum, which is unique for elements that have many natural isotopes, can also be used to
identify the various elements present. Once a chemical formula has been matched to the
spectrum, the molecular structure and bonding can be identified, and must be consistent with the
characteristics recorded by GC-MS. Typically, this identification is done automatically by
programs which come with the instrument, given a list of the elements which could be present in
the sample.
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Figure 1: Schematic of a Gas Chromatograph Mass Spectrometer

Experimental Design
In this experiment the independent variables were the standard volumes of the mixtures
in the samples. Dependent variables included the mass of the sample, mass of each component in
the sample, and the area of each component on the gas chromatograph output. Standard volumes
were varied between 100 and 900 microliters for A and B while C was only recorded at 1000
microliters. Each sample was created with a final volume of 1000 microliters.
Individual masses and mass percentages of the components in each sample containing A
and B were calculated using the known compositions of A and B. The mass percentages were
plotted against the percent area of the component on the gas chromatograph output and fit to a
linear model, thus determining a relation between each components mass percent and percent
area that was used to calculate the mass composition of mixture C.

Experimental Methods and Procedures

An Agilent 7890 Gas Chromatograph was used to test the compositions of various
samples prepared by the lab technicians. Each sample was created to have a final volume of 1000
microliters. Each technician prepared as set of six samples labeling them as A1, A2 etc. The first
five samples of each set consisted of the known mixtures A and B with volumes of 100, 300,
500, 700, and 900 microliters of one mixture and a complimentary volume of the other mixture.
The sixth sample in each set was solely comprised of the unknown mixture C. Masses were
recorded when each vial was empty, containing the first mixture, and containing the second
mixture. Volumes for each mixture were also recorded via pipettor. Each sample was tested in
the gas chromatograph three times.

Experimental Results
Figure 2 shows a sample of the gas chromatograph output as tabulated.
Figure 2. Gas Chromatograph output
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Vial
Sample Trial Percent Percent Percent Sum
Vial # of 1 of 2 of 3 Check

A1 1 2.45 87.123 10.427 100

A1 2 2.372 86.926 10.702 100

Figure 3 shows an example of the mass recordings taken before the samples were tested in the
gas chromatograph.
Figure 3. Mass recordings
Vial Volume Vial Volume Vial
Weight Std A Weight Std B Weight Mass Mass
Sample (empty) (micro with A (micro with B Std A Std B
Name (g) L) (g) L) (g) (g) (g)

A1 2.507 100 2.592 900 3.324 0.085 0.732

Figure 4 shows the ANOVA table calculated for the methanol model.
Figure 4. Methanol ANOVA
Source Symbol SS DF MSE F Pr > F

Model SSm 5.0525477 1 5.0525477 6941.5107 0.00001

Error SSE 1.3663316 58 0.0235574 - -

Lack of Fit SSlof 1.3262986 3 0.4420995 607.38440 0.00001

Pure Error SSE-pure 0.0400331 55 0.0007279 - -

Total SSt 6.4188793 59 0.1087946 - -

Engineering Analysis and Discussion

The primary assumption of this lab was that the gas chromatograph would output the
components in the order of methyl alcohol, isopropyl alcohol, and n-butyl alcohol.The secondary
assumption of this lab was that there is a direct linear relationship between the mass percent of a
component in a sample and the percent area recorded by the gas chromatograph.
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Mass percentages were calculated for the combinations of the known mixtures A and B
based on the initial mass recordings during sample collection. These mass percentages were then
compared to the percent area assumed respective to the components and plotted against each
other. The data was then fit to a linear trendline and the general equation of those trend lines
were used as independent models for each component.
An ANOVA was conducted for each of the three models. The models held varying
degrees of accuracy. While the model and lack of fit probabilities for all models tested came out
to be less than 0.00001 the F values show a more precise judge of the accuracies. The model for
the methyl alcohol was the least accurate with a Fmodel being 6941.510749 and a FLack of Fit being
607.3843976. The most accurate model was for n-butyl alcohol with a Fmodel being 5866.269325
and a FLack of Fit being 58.7490839. The isopropyl alcohol model held a Fmodel of 3780.007314 and
a FLack of Fit of 76.00937999.
These models are judged to be moderately accurate and some doubt behind the execution
of the procedure is due. One particular point of skepticism is the lack of a third peak in the
sample C2 tests; the known compositions of both A and B ensure three peaks, one for each
component.

Conclusions
Now that the models relating mass percent and percent area have been shown to be at
least acceptable given the results we can state their functions with some confidence. Each
function is stated with y being the mass percent of the component in the sample and x being the
percent area recorded on the gas chromatograph output.
● The methyl alcohol calibration function is y=0.0154x+0.0741
● The isopropyl alcohol calibration function is y=0.0083x+0.1244
● The n-butyl alcohol calibration function is y=0.0052x+0.0263
Using these calibration equations the unknown composition of mixture C can be calculated for
each of its samples and averaged to the values below. C is:
● 0.283388567 % mass methyl alcohol
● 0.439519183 % mass isopropyl alcohol
● 0.278205767 % mass n-butyl alcohol

References
Social Science Statistics, 2017 [P-Value from F-Ratio Calculator (ANOVA), Social Science
Statistics,http://www.socscistatistics.com/pvalues/fdistribution.aspx,September 19, 2017]