Third year Analytical Chemistry CHE32M2 on 22 October 2018

Quality Control Charts, One-way ANOVA & Two-way ANOVA

Plotting of X-bar charts, S-charts and R-charts

Defining parameters

X GA is the grand average

R A is the average range

SA is the average standard deviation

Calculating UCLs and LCLs for X-bar charts

Upper Control Limit (UCL) = X GA + A2 R A

Lower Control Limit (LCL) = X GA − A2 R A

Alternatively, SA can be used as well to calculate UCL and LCL:

Upper Control Limit (UCL) = X GA + A3 SA

Lower Control Limit (LCL) = X GA − A3 SA

The centreline is at X GA .

Calculating UCLs and LCLs for R-charts

UCL = D4 R A and LCL = D3 R A

The centreline is at R A .

Calculating UCLs and LCLs for S-charts

UCL = B4 SA and LCL = B3 SA

The centreline is at SA .

There is a way of calculating four region boundaries:

Boundary between A and B above X GA

Boundary between B and C above X GA

Boundary between A and B below X GA

Boundary between B and C below X GA

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 Table 2: The table of constants for UCLs and LCLs for X-bar charts, R-charts and S-charts

Subgroup X-bar chart

or S-chart R-chart
Replicates Using R A Using SA

n A2 A3 B3 B4 D3 D4
2 1.886 2.659 0 3.267 0 3.268
3 1.023 1.954 0 2.568 0 2.574
4 0.729 1.628 0 2.266 0 2.282
5 0.577 1.427 0 2.089 0 2.114
6 0.483 1.287 0.030 1.970 0 2.004
7 0.419 1.182 0.118 1.882 0.076 1.924
8 0.373 1.099 0.185 1.815 0.136 1.864
9 0.337 1.032 0.239 1.761 0.184 1.816
10 0.308 0.975 0.284 1.716 0.223 1.777
11 0.285 0.927 0.322 1.678 0.256 1.744
12 0.266 0.886 0.354 1.646 0.283 1.717
13 0.249 0.850 0.382 1.619 0.307 1.693
14 0.235 0.817 0.407 1.593 0.328 1.672
15 0.223 0.789 0.428 1.572 0.347 1.653

Question 2 [20 marks] ... from 2014 CHE32M2 Chemometrics Test

Specifications require the nickel content of manufactured stainless steel hydraulic valves to
be 13% by weight. To monitor the production process, four valves were selected from the
production line each hour over an 8-hour period and the percentage nickel content was
measured for each, with the results recorded in Table 2 below.

Hour Nickel Content

1 13.1 12.8 12.7 12.9

2 12.5 13.0 13.6 13.1
3 12.9 12.9 13.2 13.3
4 12.4 13.0 12.1 12.6
5 12.8 11.9 12.7 12.4
6 13.0 13.6 13.2 12.9
7 13.5 13.5 13.1 12.7
8 12.6 13.9 13.3 12.8

(a) Make an appropriate table of results which enables you to draw an X-bar chart and a
Range chart. [5 marks]

(b) Show the calculations of the upper control limit (UCL) and lower control limit (LCL) for an
x-bar chart.

[5 marks]

(c) Plot an X-bar chart and label it accordingly.

[10 marks]

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Question 3 [15 marks] ... from 2014 CHE32M2 Chemometrics Test

(a) Using the results in Question 2 above, show the calculations of the upper control limit
(UCL) and lower control limit (LCL) for an R chart.

[5 marks]

(b) Using the data in Question 2 above, plot an R-chart for the range and label it accordingly.

[10 marks]

Summary - constructing a Shewhart chart

2(standard deviation)
Warning lines are at: mean ±
√n
3(standard deviation)
Action lines are at: mean ±
√n
n is the number of replicates! (n=2 for duplicates, n=3 for triplicates, n=4 for quadruplicates,
n=5 for quintuplicates, n=6 for sextuplicates n=7 for septuplicates, n=8 for octuplicates, n=9
for nonuplicate and n=10 for decuplicates).

Question 4 [15 marks] ... from CHE21M2 exam on 27 Nov 2014

The ascorbic acid concentration of five different brands of orange juice was measured. Six
replicate samples of each brand were analyzed. The following partial ANOVA table was
obtained (Table 1).

Table 1 for Question 4

Degrees of
Source of Variation Sum of Squares Mean Squares F-ratio
Freedom

Treatments of juices 8.45

Residual of juices 0.913

Total

(a) Fill in the missing entries in the Table.

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 [3 marks]

(b) State the null and alternate hypotheses.

[2 marks]

(c) Is there a difference in the ascorbic acid concentration of the five juices at the 95%
confidence level?

[2 marks]

Results in Table 2 were obtained during the manufacturing of an engineering plastic, in which
a laminate was sampled and put into a machine to test for strength. Laminates were taken
once a shift from the production line, and the results shown in Table 2 relate to ‘transverse
flexure strength’ (TFS).

Table 2: Engineering plastic strength data for a Shewhart chart

Transverse Flexure Strength

Shift
(TFS) / arbitary units

1 137.8
2 140.5
3 139.6
4 143.4
5 137.6
6 142.0
7 137.5
8 143.1
9 138.6
10 142.8
11 138.4
12 139.3
13 139.0
14 142.4
15 138.6

(d) Calculate (correct to 3 decimal places) the mean ‘transverse flexure strength’ (TFS).

[1 mark]

(e) Calculate the standard deviation of the above data (correct to 3 decimal places).

[1 mark]

(f) Calculate the warning limits and action limits for Shewhart chart of the above data.

[2 marks]

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(g) Use the above data to construct a Shewhart chart. Given that in this case the analysis was
done in triplicates, indicate the positions of warning and action lines on your chart.

[Graph: 3 marks]

(h) Basing on your chart in (g) above, should the quality control manager intervene in this
process? Explain your answer clearly.

[1 mark]

CHE32M2 ANOVA Questions ... August 2015

Question 8 [10 marks] ... from Supp CHE32M2 on 16 Jan 2015

Begin this question on a new page.

A major distributor of 50-mℓ burettes in the Eastern Cape suspects that consumers are
insensitive to price changes for the highest-quality 50-mℓ burette. To test this suspicion, 4
laboratory glassware suppliers are selected at random and asked to sell the 50-mℓ burettes
at 1 of 4 predetermined prices. After 4 weeks, the number of 50-mℓ burettes sold each week
is shown in Table 3:

Table 3 for Question 7

Price 1 Price 2 Price 3 Price 4

3 5 10 8
5 4 9 4
7 6 4 5
4 7 5 7

What conclusions can be made about the population mean selling price at the 0.05 level of
significance?

[10 marks]

Important ANOVA Equations

G – grand total of all experimental observations

N = rt = product of replicates and treatments = total number of measurements

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 G G
ybar = ỹ = = = grand mean of the whole experiment.
N rt
Ti - total yield of all the replicates which carried the treatment i. Said differently, Ti is the sum
of the measurements in the ith sample.

S – total sum of squares

t r
2 G2
S = ∑ ∑(yij ) −
N
i=1 j=1

ST - sum of squares for Treatments

t
1 G2
ST = [ ∑(Ti )2 ] −
r N
i=1

SE - residual sum of squares = difference between S and ST . Meaning, 𝐒𝐄 = 𝐒 − 𝐒𝐓 .

G2
At times ( ) is called CM, correction for mean. Please remember that!
N

Table 1: Analysis of variance for a completely randomised design [One Way ANOVA]

Degrees of
Source of variation Sum of Squares Mean Square F-ratio
Freedom

𝐒𝐓 𝐓𝐫𝐞𝐚𝐭𝐦𝐞𝐧𝐭 𝐌𝐞𝐚𝐧 𝐒𝐪𝐮𝐚𝐫𝐞

= 𝐅 (𝐭−𝟏),𝐭(𝐫−𝟏) = 𝐅𝐜𝐚𝐥
Treatments t-1 ST 𝐭−𝟏 𝐑𝐞𝐬𝐢𝐝𝐮𝐚𝐥 𝐌𝐞𝐚𝐧 𝐒𝐪𝐮𝐚𝐫𝐞

𝐒𝐄
Residual t(r-1) SE 𝐭(𝐫 − 𝟏)

Total rt-1 S

Question 6 [10 marks]

Begin this question on a NEW page.

The number of grams of fibre per serving for a random sample of three different kinds of foods
is listed below in Table 6.1*.

Table 6.1: Grams of fibre per serving in various foods

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 Breakfast cereals Fruits Vegetables

3 5.5 10
4 2 1.5
6 4.4 3.5
4 1.6 2.7
10 3.8 2.5
5 4.5 6.5
6 2.8 4
8 3
5

* Source: The Doctor’s Pocket Calorie, Fat, and Carbohydrate Counter.

Is there sufficient evidence at the 0.05 level of significance to conclude that there is a
difference in mean fibre content among breakfast cereals, fruits, and vegetables?

[10 marks]

::::::::::::::::::::::::::::

Two way ANOVA for randomised block design

Brief Introduction...

A randomized block design usually provides more information per observation than the
amount contained in a completely randomised design.

Task: Suppose the IT manager for Nedbank (Ngebs City branch) wants to compare the length
of time required to process the bank’s daily receipts using 3 different computer programs, A,
B, and C. A completely randomized design can be achieved by selecting 15 days and
randomly assigning the receipts for 5 days to be processed using each of the programs.

A better way to conduct this experiment so that more information on the mean processing
times is made available is to use the receipts for only 5 days and process the data for each
day using each of the three programs. This randomized block procedure acknowledges the
fact that the length of time required to process a day’s receipts varies substantially from day
to day depending on the level of the day’s business (is it month-end during the week or is it
month-end on Saturday or is it just before a public holiday), the complexity of the transactions,
etc etc. By comparing the processing time for each day, Nedbank eliminates day-to-day
variation from the comparison. This elimination is the blocking part in two way ANOVA.

The randomized block design described above is shown diagrammatically below in Figure 1.
Clearly there are 5 jobs and each job can be viewed as a block of 3 experimental units, that is
runs on the computer, one corresponding to the use of each of the programs, A, B, and C.
These blocks are said to be randomized because the treatments (computer programs) are
randomly assigned to the experimental units within a block. The programs used to process a

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day’s receipts are run in a random order so as to avoid bias introduced by other unknown and
unmeasured variables that may affect the processing time.

Figure 1: Diagram of a randomized block design containing 3 treatments and 5 blocks.

Key point: Generally, a randomized block design to compare p treatments will contain b
blocks, with each block containing p experimental units. Each treatment appears once in every
block with p treatments randomly assigned to the experimental units within each block.

A careful analysis will show that S and SB (blocks sum of squares) are the same as for a
completely randomised layout.

Recapping...

S – total sum of squares

t r
2 G2
S = ∑ ∑(yij ) −
N
i=1 j=1

ST - sum of squares for Treatments

t
1 G2
ST = [ ∑(Ti )2 ] −
r N
i=1

SE - residual sum of squares = difference between S and ( SB + ST ).

Meaning, 𝐒𝐄 = 𝐒 − 𝐒𝐁 − 𝐒𝐓 .

Here are new terms that have to be defined:

B
Bj = the total of all yields of plots in block j. Therefore, the mean yield in block j = tj. Remember,
the block contains t plots.

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SB is the blocks sum of squares. SB will have (r − 1) degrees of freedom.
r
1 2 G2
SB = ∑(Bj ) − or
t N
j=1

r
1
SB = (r ∑ Bj2 − G2 )
N
j=1

Table 2: Analysis of variance for a randomised block design [Two Way ANOVA]

Degrees of
Source of variation Sum of Squares Mean Square F-ratio
Freedom

Between-blocks (r-1) SB

Between-treatments (t-1) ST

Residual (r-1)(t-1) SE = S - SB - ST

Total (rt-1) S

Question 1 [15 marks]

Begin this question on a new page.

In an experiment to compare the percentage efficiency of different chelating agents in

extracting Zn2+ ions from aqueous solution, the results in Table 1.1 were obtained.

Table 1.1: Percentage efficiency of different chelating agents in extracting Zn2+ ions from
aqueous solution.

Chelating agent

Day A B C D E

1 80 81 77 80 83
2 78 79 80 81 79
3 82 83 78 83 80
4 77 80 83 78 78

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On each day a fresh solution of the Zn2+ ions (with a specific concentration) was prepared and
the extraction performed with each of the chelating agents taken in random order.

(a) Test at 95% confidence level to see whether the different chelating agents have
significantly different extraction efficiencies.

[10 marks]

(b) Test at 95 % confidence level to see whether the day-to-day variation is significantly greater
than the variation due to the random error of measurement.

[5 marks]

Question 7 [15 marks] ... from CHE32M2 27 Nov 2014 exam

Begin this question on a new page.

(a) Deviations from Beer’s law are often divided into three categories, which are:

 Real deviations
 Chemical deviations
 Instrumental deviations

Write brief but concise notes on

(i) chemical deviations from Beer’s law, and

(ii) instrumental deviations from Beer’s law.

Where necessary, include equations and/or diagrams.

[2 marks + 3 marks]

(b) Explain the difference between repeatability and reproducibility.

[2 marks]

(c) ANOVA question removed!

[8 marks]

Question 4 [20 marks] ... from CHE32M2 Chemometrics Test in 2014

Begin this question on a new page.

Vusi Dhlomo, a WSU lecturer, claims that television-viewing habits are the same for all
students in different undergraduate years at NMD campus. He questioned a random sample
of students about how many minutes they watch TV each day after lectures and until bedtime,
and produced the following data in Table 3:

Table 3: Data for Question 4

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 First Years Second Years Third Years

459 115 272

311 153 88
152 201 374
293 30 178

(a) Conduct an ANOVA test at the 0.01 level to test Vusi Dhlomo’s claim.

The examiner must be able to follow your hypothesis testing and your statistical
decisions/arguments.

[15 marks]

(b) What is the conclusion when you conduct the ANOVA test at the 0.05 level to test Vusi
Dhlomo’s claim.

[5 marks]

Please look for a power-point I sent out last year (2017) to second years and third years. That
power-point is on the first part of Chemometrics.

Please know that Chemometrics power-point (inside out)!

As the lecturer, I am assuming that you know the following (covered in CHE21M2):

 Q-test
 Student t-test and
 F-test

Here are Statistical Tables you may want to refer to.

Statistical Tables....

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