Week

 2  
Sample  prepara,on-­‐con$nued  

Week  2   1  
 Preparing  solu2ons  
How  to  prepare  a  solu,on?    
 
Expression  of  concentra,on    
 Concentra,on  is  the  quan,ty  of  solute  in  a  known  amount  of  
volume  or  mass  of  solu,on  or  solvent  
 Concentra,on  =          Amount  of  solute  
                                                 Amount  of  solu,on  

Unit  for  concentra,ons  

•  Molarity  (M)  –  mole  of  solute/litre  of  solu,on  
•  Molarity  (m)  -­‐  moles  of  solute/kilogram  of  solvent.  
•  Normality  (N)  (not  common)  –  can  only  be  calculated  when  we  deal  with  
reac,ons,  because  normality  is  a  func,on  of  equivalents.  
•  Parts  per  million  (ppm)  –  miligram  of  solute/litre  of  solu,on  
•  Parts  per  billion  (ppb)  –  microgram  of  solute/litre  of  solu,on  
•  Percent  concentra,on  (%w/w,  %w/v,  %v/v)  

Week  2   2  
 Concentra,on  in  terms  of    
percent  composi,on  
The concentration of substance in commercial aqueous reagents, organic
solvents and commercial household products are usually expressed in
percent composition

•  Weight percent = Weight of solute x 100%

(%w/w) Weight of solution

• Volume percent = Volume of solute x 100%

(%v/v) Volume of solution

• Weight-volume = Weight of solute x 100%

(%w/v) Volume of solution

Example: 37% is labeled on a HCl reagent bottle. This means that it contains 37 g
HCl per 100 g solution

Week  2   3  
    
•    Parts  per  million  (ppm)    =  g  solute  
                               106  g  solu2on  
     Or      =        µg/g  
   
 
As  the  density  of  aqueous  solu,on  oPen  very  close  to  1.00  g/L,  we  usually  
             correlates  1  g  water  with  1  mL  water  (approxima,on)  
 
             Therefore,  1  ppm  =  1  µg/g can also be converted to 1 µg/mL  =  1  
mg/L      
 
 
   

Week  2   4  
 For  trace  analysis  in  liquid  sample  
~Analysis  of  very  very  very  liLle  amount  of  analytes  

•  Parts  per  billion  (ppb)      =    g  solute  

                     109  g  solu2on  
 Therefore,1  ppb  =  1  ng/g = 1 ng/mL  =  1  µg/L  
 
•  Parts  per  trillion  (ppt)      =    g  solute  
                     1012  g  solu2on  
 Therefore,1  ppt  =  1  pg/g = 1 pg/mL  =  1  ng/L  

 
 

Week  2   5  
 Conver,ng  percent  composi,on  to  molar  concentra,on  
-­‐conver$ng  ‘commercial  term’  to  ‘easier  laboratory  term’-­‐  
•  Example:    
 A  commercial  aqueous  ammonia  (NH3  )  boYle  is  labeled  as  28.0%  w/w,  
and  has  a  density  of  0.899  g/mL  and  MW  of  17.03  g/mol.  Let  say  you  want  
to  convert  the  concentra,on  into  molarity  for  easier  calcula,on  in  your  
lab  book,  how  can  you  do  that?    
  density  
=  28  g/100  g                x            0.899  g/mL  
 
=  0.2517  g/mL  
 
=  0.2517  g/mL            /              17.031  g/mol   MW  
 
=  0.01478  mol/mL              x              1000  mL/1L    
 
=  14.8  mol/L                or  14.8  M  

6  
Week  2   6  
 Prepara,on  of  solu,on  
 Example:    How  to  prepare  250  mL  of  0.100  M  NaOH  from  NaOH  
solid?  [MW:  NaOH  =  40  g/mol]  

 
1.  Calculate  the  weight  (g)  of  NaOH  pellet  using  MW  to  produce  0.1  M  
solu,on  
 Calcula$ons  ????  
2.      Weigh  ???  g  of  solid  (generally  ±  0.1  mg,  ie  up  to  4  decimal  places  in  
grams)  
3.  Dissolve  in  water,  transfer  (quan,ta,vely  with  rinsing)  to  a  250  mL  
volumetric  flask,  and  dilute  to  the  mark  

Dissolve  and  
Calculate   Weigh  
transfer  

Week  2   7  
 Prepara,on  of  solu,on  
 Example:    How  to  prepare  25  mL  of  0.01  M  glutamic  
acid  solu,on  from  glutamic  acid  powder?  [MW:  
Glutamic  acid  =  147.13  g/mol]  

0.03678 g

Week  2   8  
 Dilu,on  of  solu,on  
The  moles  solute  in  concentrated  (1)  solu2on  equals  the  
moles  in  dilute  (2)  solu2on  

∴ M1 × V1 = M2 × V2

M1  :  Ini,al  concentra,on  of  solu,on  

V1  :  Volume  of  concentrated  solu,on  transferred  
M2  :  Concentra,on  of  final  solu,on  (diluted)  
V2  :  Volume  of  final  standard  solu,on  

Example:    Describe  the  prepara,on  of  50  mL  of  0.100  M  NaOH  
solu,on  from  a  0.5  M  solu,on  
 
Calcula,ons…    
How  to  ???…  ?    
Glassware  requirement:  ??  mL  pipet  and  ??  mL  volumetric  flask  

Week  2   9  
 Week  2+3  
CHAPTER  2  
Data  analysis  and  sta,s,cs  

Week  2   10  
 Statistics in Analytical Chemistry

• Statistical methods enables a chemist to base

assessment on fewer data (generally>25) or data
accumulated from the analysis of similar
samples
• The problem is examined with respect to
precision, accuracy and reliability required of
the results
• Analysis of the results obtained are resolved into
two stages:
- examination of the reliability of the results
- assessment of the meaning of the results

Week  2   11  
 ie. measurement of agreement between experimental
mean and true value (which may not be known!)
Measures of accuracy:
- Absolute error: E = xi - µ
(where µ = true or accepted value)

xi − µ
- Relative error: E R = | | × 100%
µ
ACCURACY   Relative error is more useful in practice
• degree  of  agreement  between  measured  value  
• Absolute  error  =  measured  value  –  true  value  
and  the  true  value  (which  may  not  be  known!)   E.g.  if  a  2.72  g  sample  is  analysed  to  be  2.62g,  
• Therefore,  it  is  the  degree  of  agreement   the  absolute  error  is  -­‐0.10g    
between  measured  value  and  the  accepted  true    
value   • Rela,ve  error  is  the  absolute  error  expressed  
as  %  of  the  true  value  
PRECISION   E.g.  (-­‐0.10g/2.72  g)  x  100%  =  -­‐3.7%  
• Degree  of  agreement  between  replicate  
measurements  of  the  same  quan,ty;  repeatability  
of  a  result.  
• Expressed  by  standard  devia$on,  the  coefficient  of  
varia$on,  the  range  of  the  data  or  as  confidence  
interval  (e.g.  95%)  about  the  mean  value    
• How  similar  are  values  obtained  in  exactly  the  
same  way?  
• Useful  for  measuring  devia,on  from  the  mean.  

di = x i − x
Week  2   12  
High  Precision  
High  accuracy  
 

High  precision  
Low  accuracy  

Low  precision  
Low  accuracy  

Low  precision  
High  accuracy  

x
Week  2   13  
 Types  of  error  in  chemical  analysis  
 
A.  Systema2c  (determinate)  Error  
Operator/Instrument  error/Method  error    
• Can  be  constant  (e.g  uncalibrated  weight  used  in  all  weighing)  or  variable  (e.g.buret  whose  
volume  readings  are  in  error  by  different  amount  at  different  volumes)  
• Readings  all  too  high  or  too  low  that  can  affect  accuracy.    
How  to  detect?àblank  determina,ons,  analysis  of  standard  samples,  independent  analyses  
by  alterna,ve/dissimilar  methods    
 B.  Random/accidental  (indeterminate)  Error  
 • Represents  experimental  uncertainty  occurred  in  any  measurement  
 • Random  and  cannot  be  avoided.  Affects  precision,  can  only  be  
controlled  
• Revealed  by  small  differences  in  successive  measurements  made  by  
the  same  analyst  under  iden,cal  condi,onsà  can’t  be  predicted/
es,mated  but  can  be  dealt  with  sta*s*cs  
• Data  scaYered  approximately  symmetrically  about  a  mean  value.  
 
C.  Gross  Errors  
• Serious  but  very  seldom  occur  in  analysis.  
• Usually  obvious  -­‐  give  outlier  readings.  
• Detectable  by  carrying  out  sufficient  replicate  measurements.  
• Experiments  must  be  repeated.  
e.g.  Instrument  faulty,  contaminated  reagent  

Week  2   14  
 SOURCES  OF  SYSTEMATIC  ERROR  

*Ways to minimize/eliminate systematic errors

• Instrument errors:
- Careful recalibration and good maintenance of
apparatus (eg
(eg glassware) and instruments ((eg
eg
AAS, GC)
• Method errors:
- Analysis of certified standard reference
materials (SRM)
- Use 2 or more independent methods
- Analysis of blanks
• Personal errors:
- Training of operator, care and self-
self-discipline

Week  2   15  
 Significant  figures  (SF)  
• The  SF  of  a  number  are  those  digits  that  carry  meaning  contribu,ng  to  its  precision.  
•   Zero  is  significant  only  when:  
A.  It  occurs  in  the  middle  of  a  number.  Examples:  
a)  401      -­‐  3  SF  
b)  6.0015    -­‐  5  SF  
c)  3.00      -­‐  3  SF  
d)  6.00  ×  102    -­‐  3  SF  

Rounding  off  in  the  step  of  addi,on  &  subtrac,on  

• Use  the  same  number  of  decimal  places  (dp)  as  the  number  with  the  fewest  
decimal  places.  Example:    
   12.2      +      0.365      +      1.04    =      13.605      
 (1  dp)            (3  dp)                (2  dp)                                              
  =  13.6  (1  dp)  
 
SF  in  mul,plica,on    &Division   40.1 × 0.1633 −2
• Use  the  same  number  of  digits  as   = 3.21 × 10 (3 sf )
 the  number  with  the  fewest  number   204 . 228
 of  digits.  

Week  2   16  
 Basic Statistical Concepts/Definitions
• True value - value that remains unknown except
when a standard sample is analyzed
(value estimated from results of varying precision
depending on the method used)
• Accuracy - nearness of a measurement or result
to the true value (expressed in terms of error
error))
• Precision - variability of a measurement
(Standard deviations are precision indicators)
• Spread-- difference between the highest and
Spread
lowest results in a set (spread is a measure of
precision)
• Mean - average of a replicate set of results
• Median - middle value of a replicate set of results

Week  2   17  
• Degree of Freedom - number of results in a set
(each time another quantity is derived from the
set, the degrees of freedom are reduced by 1)
• Range - difference between the highest and
lowest value of the results
• Standard Deviation (s or σ) - difference, with
respect to sign, between an individual result
and the mean or median of the set
• Relative Standard Deviation (RSD) - Also known
as the coefficient of variation, often used in
comparing precisions
• Variance (V)
(V) - square of the value of standard
deviation (σ2 or s2)

Week  2   18  
Mean/Average   Median  
N
•  Arranged  in  accending  order,  if  data  in  the  
middle  in  an  odd  number  record  it  as  the  
∑ x i it  If  is    for   large  data  set,  
called  popula,on   median.  
 
x = i =1 mean  (µ)  
 
N  
Xi    =    individual  values  of  x     •  Arranged  in  ascending  order,  if  two  middle  
N  =    number  of  replicate  measurements     data  are  even  numbers  then  average  the  
two  numbers  
 
Range      
The  difference  between  the  highest  
and  lowest  result.  

Week  2   19  
 Standard  Devia,on  (SD)    
–  a  very  important  precision  indicator  
Measure  of  spread  about  the  mean  
Es,mate  the  variability  of  individual  measurement  (The  standard  devia,on  is  beYer  es,mated  
by  the  pooling  of  results  from  more  than  one  set)    
Can  be  calculated  using  Excel  spreadsheet  
Small  sample  size  (N=20)   Popula2on  (N=  >20)    

s =
(
∑ xi − x )
σ=
∑ xi − µ ( )2
N−1 N
Xi    =    individual  values  of  x     Xi    =    individual  values  of  x    
 x        =  mean    x        =  popula,on  mean  
N  =    number  of  replicate  measurements     N  =    number  of  replicate  measurements    

Smaller  SD  means  more  precise  the  analysis  is  

Week  2   20  
 ! RELATIVE STANDARD DEVIATION (RSD)/
COEFFICIENT OF VARIATION (CV)
Standard deviation divided by mean
(depends on the units used)

Rela2ve  Standard  Devia2on  (RSD)  

Varian,  V   !VARIANCE
–  also  a  very  important  precision  
The square of standard deviation
  indicator   30):
- Sample variance (≤ 30) V = s2
The  square  of  standard  devia,on.     - Population variance (large #)
s #):: V = σ2
For  sample,    V    =    s2     RSD = × 100%
x
N Acceptable  RSD  %  depends  on  the  
( x x ) 2 type  of  analysis.  I.e.  
∑ i −
• Trace  analysis,  RSD  %  should  be  <5%  
s 2 (V ) = i =1
• Environmental  analysis  <15%  
N −1
• Pharmaceu,cal  analysis  <10  %  
 

Week  2   21  
 Sample Se (mg/g) (xi - mean)
Example: 1 0.07 4.9x10-5
Determine the 2 0.07 4.9x10-5
content of Se in 3 0.08 9.0x10-6
a batch of 4 0.07 4.9x10-5
brown rice 5 0.07 4.9x10-5
6 0.08 9.0x10-6
7 0.08 9.0x10-6
Mean = Σxi/N 8 0.09 1.69x10-4
= 0.077 9 0.08 9.0x10-6
Σ(x
xi-mean)2 = 4.01x10-4

∑ i
( x − x ) 2

S.D. = s= i = 0.007
N −1
Content of Se = 0.077 ± 0.007 mg/g
What does this result mean?
Week  2   22  
 10.00 10.07 10.07 10.03 10.13
10.00 10.08 10.00
10.24 10.05 10.24
10.08 10.22 10.05 10.22

MEAN 10.00 10.10

MEAN Confidence  
9.90
10.00 10.1010.01
limits  10.01
9.90 (CL)  a10.01
10.01
nd  confidence  
0.00 interval   (0.25
CI)–  h0.03
ow  sure  
0.17are  you?  
STD DEV 0.00 0.01 0.25 0.03 0.17
STD DEV 0.01

• Calcula,on  of  SD  for  a  set  of  data  provides  indica,on  of  the  precision  inherent  in  
par,cular  procedure.    
CONFIDENCE LIMIT & CONFIDENCE INTERVAL
• For  large  
• Confidence data  set,  
Interval (CI) it  disoesn't   the range give  of
any   info  about  how  close  the  experimentally  
values
determined  
surrounding themmean ean  (,            within
mean, )to  the  which
true  m ean  value  (µ).  
the
population mean, CONFIDENCE
µ is expected to LIMITlie with& CONFIDENCE
a INTERVAL
certain degree of probability
• The boundries • Confidence
of the range are Interval
called the (CI) is the range of values
Confidence Limits surrounding the mean mean,, within which the
• Confidence Level (CL) is themean,
population probability µ isthat the
expected to lie with a
true mean lies within a certain interval
(expressed ascertain %) degree of probability
Example: • The boundries of the range are called the
It is 99% probable Confidence
that µ forLimits a set of
measurement is 7.25mg ± 0.15.
• Confidence Level Thus, theis
(CL) meanthe probability that the
should lie in the interval from 7.10mg to 7.40mg
with 99% probability true mean lies within a certain interval
(expressed as %)
Example:
It is 99% probable that µ for a set of
measurement is 7.25mg ± 0.15. Thus, the mean
should lie in the interval from 7.10mg to 7.40mg
with 99% probability
Values of z for determining confidence limits
Week  2   23  
Confidence level (%) z
 Confidence  interval  for  small  data  set  (N  =  20)  

ts •   Values  of  t  depend  on  degree  of  freedom,  v  (N  -­‐  1)  and  
CI ( µ ) = x ± confidence  level  (from  Table).  
N  
•   t  also  known  as  ‘student’s  t’  and  will  be  used  in  
N=Number  of  measurements/
replicates   hypothesis  test.  

t=Student’s  t  values  (constant  and   Values of t for various levels of probability

given)  
Degrees of Freedom 80% 90% 95% 99%
s=  SD   (N
(N--1)

1 3.08 6.31 12.7 63.7

  2 1.89 2.92 4.30 9.92
3 1.64 2.35 3.18 5.84
4 1.53 2.13 2.78 4.60
5 1.48 2.02 2.57 4.03
6 1.44 1.94 2.45 3.71
7 1.42 1.90 2.36 3.50
8 1.40 1.86 2.31 3.36
9 1.38 1.83 2.26 3.25
19 1.33 1.73 2.10 2.88
59 1.30 1.67 2.00 2.66
∞ 1.29 1.64 1.96 2.58

Week  2   24  
 Example:  
 
Data  for  the  analysis  of  calcium  in  rock  are  given  by  14.35%,  14.41%,  14.40%,  14.32%  and  
14.37%.  Within  what  range  are  you  95%  confident  that  the  true  value  lies??  
ts
CI ( µ ) = x ±
Solu,on:  
N
Mean,  x          =    14.37  
SD,  s    =    0.037   At  different  confidence  level,  
From  the  table,  at  95  %  confidence  level,    
N  -­‐  1  =  4,  t    =    2.78.   Confidence Level Confidence Interval
  2.78 × 0.037 90% µ = 14.37% ± 0.04
µ=x±
Therefore,  CI  is  :   5 95% µ = 14.37% ± 0.05
= 14.37% ± 0.05% 99% µ = 14.37% ± 0.08
Summary:  
So  you  are  95%  confidence  that  (in  the   If  the  confidence  level  increased,  the  
absence  of  determinate  error),     confidence  interval  (CI)  also  increased.  The  
the  true  value  falls  within  14.32%  to  14.42%   probability  of  the  true  mean  value  (µ)  appeared  
in  the    interval  will  increase  

Week  2   25  
The  concentra,on  of  an  addi,ve  in  a  standard  sample  of  gasoline  was  
measured  5  ,mes  with  the  following  results:  0.13,  0.11,  0.12,  0.20,  and  0.14  %  by  mass.  
 
(a)  Calculate  the  sample  mean  and  standard  devia,on  of  the  data  
Mean:  0.14,  s:  0.03536  
 
(b)  Calculate  the  95%  confidence  interval  and  explain  what  does  the  data  means?  
 
  ts
CI ( µ ) = x ±
  N
2.78 × 0.03536
µ=x±
5 there  is  a  95%  probability  that  the  
concentra,on  will  fall  between  0.10%  to  0.18%  
= 0.14% ± 0.04%

Week  2   26  
 Confidence  interval  for  large  data  set  (N  >20)  
essions of Confidence
  Interval
• CI  when  σ  is   Values of z for determining confidence limits
rge no. of data (>30)
µ = x ± z kσnown  (popula,on),    
own population std
N Confidence level (%) z
n, σ zσ
(≤30)
mall no. of data (≤ µ=x±
µ=x± ts
50 0.67
knowing σ (know s) N N 68
80
1.0
1.29
90 1.64
N  =  Number  of  measurements/replicates  
mber of measurements
95 1.96
ues from normal distribution curve
96 2.00
z-table)z=  the  value  from  the  standard  normal  
om the z-
99 2.58
ues from normal distribution curve but
distribu,on  
on the degree of freedom (N- (Nfor  
-1)t(Read
he  selected  confidence  level     99.7 3.00
99.9 3.29
e t-
t-table) At 90% confidence level, z = 1.64,
known as the ‘student’s t’, generally
hypothesis tests σ
µ = x ± 1.64
N

At 95% confidence level, z = 1.96,

σ
µ = x ± 1.96
N

At 99% confidence level, z = 2.58, σ σ

x − 2.58 < µ < x + 2.58
µ = x ± 2.58
σ or,   N N
N
Week  2   27  
 Other  usage  of  confidence  interval  (CI)  

OTHER USAGE OF CONFIDENCE INTERVAL

• To determine # of replicates (N) needed for the
the mean to be within the confidence interval
• To determine systematic error

Week  2   28  
 A.  To  determine  numer  of  replicate  

Exa
gav
Example 1:
1: Calculate the number of replicates A so
needed to change the confidence interval by whe
1.5 µg/mL at 95% confidence level. con
Given, s = 2.4 µg/mL
At 9

Values of t for various levels of probability

Degrees of Freedom 80% 90% 95% 99%

(N
(N--1)

1 3.08 6.31 12.7 63.7

2
3
1.89
1.64
2.92
2.35
4.30
3.18
9.92
5.84
This
4
5
1.53
1.48
2.13
2.02
2.78
2.57
4.60
4.03
time
6
7
1.44
1.42
1.94
1.90
2.45
2.36
3.71
3.50
0.46
8
9
1.40
1.38
1.86
1.83
2.31
2.26
3.36
3.25
The
19
59
1.33
1.30
1.73
1.67
2.10
2.00
2.88
2.66 rang
∞ 1.29 1.64 1.96 2.58

Week  2   29  
Sample Question
(Confidence Limit when s is known)
 B.  To  determine  systema2c  error  
1)  Calcula2on  method  1  
Example  
A  standard  solu,on  gave  an  absorp,on  reading  of  0.470  at  a  par,cular  wavelength.  
Ten  measurements  were  done  on  a  sample  and  the  mean  gave  a  value  of  0.461,  
with  standard  devia,on  (s)  of  0.003.  Show  whether  systema,c  error  exists  in  the  
measurements  at  95%  confidence  level.  
  Values of t for various levels of probability
Solu,on   Degrees of Freedom 80% 90% 95% 99%
At  95%  confidence  level,  N  =  10,  t  =  2.26,     (N
(N--1)

1 3.08 6.31 12.7 63.7

2 1.89 2.92 4.30 9.92
ts 3 1.64 2.35 3.18 5.84
CI ( µ ) = x ± 4
5
1.53
1.48
2.13
2.02
2.78
2.57
4.60
4.03
N 6
7
1.44
1.42
1.94
1.90
2.45
2.36
3.71
3.50
8 1.40 1.86 2.31 3.36

= 0.461 ± 2.26
(0.003) 9
19
1.38
1.33
1.83
1.73
2.26
2.10
3.25
2.88
10 59
∞
1.30
1.29
1.67
1.64
2.00
1.96
2.66
2.58

= 0.461 ± 0.002
The  calcula,on  gives  confidence  limit  of,   • Does  the  true  mean  0.470  
 0.459  <  µ  <  0.463   belong  to  the  interval?  
Sample Question
• D(Confidence
oes  systema*c   error  
Limit when s is p resent?    
known)
AAS analysis of Cu in aircraft engine oil gave a mean value of
8.53 mg Cu/mL
Cu/mL.. Pooled results of many analyses showed
that s → σ = 0.32 mg Cu/mL
Cu/mL.. Calculate the confidence
Week  2   30  
intervals (CI) at 90% & 99% confidence levels based on
(a) 1 (b) 4 (c) 16 measurements
(a) Confidence limit (CL) = µ = x ± t s
 B.  To  determine  systema2c  error  
2)  Calcula2on  method  2  
Example  
A  standard  solu,on  gave  an  absorp,on  reading  of  0.470  at  a  par,cular  wavelength.  
Ten  measurements  were  done  on  a  sample  and  the  mean  gave  a  value  of  0.461,  
with  standard  devia,on  (s)  of  0.003.  Show  whether  systema,c  error  exists  in  the  
measurements  at  95%  confidence  level.  
 
Solu,on  
At  95%  confidence  level,  N  =  10,  t  =  2.26,    
N The  tcalc  >ttable  
± t = (x − µ )  
s Does  systema*c  error  
10 present?    
= (0.461 − 0.470)  
0.003
t = 9.49

Week  2   31  
 0.463 N 10
Therefore, the
the reading 0.470 is
= 0.461 ± 0.002 NOT in the
range, and systematic
This means,error
0.459EXISTS
< µ < 0.463, ie 95% of the
time, the true value lies between 0.459 to
0.463
Therefore, the
the reading 0.470 is NOT in the
range, and systematic error EXISTS

STRIBUTION OF ERRORS Based on the curve, percentages of area

DISTRIBUTION
GAUSSIAN distribution (bell shaped, OF ERRORS under the curves between
Based on certain
the curve, limits
percentages of area
curve) gives limits within
NORMAL or which
GAUSSIAN thedistribution (bell shaped, of z are as follows:
under the curves between certain limits
(µ) is expected
ean (µ to lie with a given of z are as follows:
symmetrical curve) gives limits within which the 50% of area lies between ±0.67s
population mean (
(µµ) is
obability (without any systematic error) expected to lie with a given 50% of area lies between ±0.67s
degree of probability (without any systematic error)
80% 80%
" "
±1.29s±1.29s
90% 90% " " ±1.64s±1.64s
80% 50% 95% 80% 95% 95% 95% " " ±1.96s±1.96s
99% 99% " " ±2.58s±2.58s
-0.67s +0.67s +1.29s -1.96s +1.96s
-1.29s +1.29s -1.96s -1.29s
+1.96s When we say that ‘at a confidence level of
When we say that
80%, ‘at
the a confidence
confidence level
limits are of we
±1.29s’
mean that: limits are ±1.29s’ we
80%, the confidence
dN/N

dN/N
dN/N

mean that:- 80% of the time the true mean will lie
dN/N

dN/N

between
- 80% of the time the±1.29s
true of the measurements
mean will lie made
- or in other words 20% of the time the true
υ υ υ between ±1.29smeanof the
will NOTmeasurements
lie between ±1.29s made
υ
-3s -2s -1s 0 1s 2s 3s 4s -4s -3s -2s -1s 0 1s 2s 3s 4s -4s -3s -2s -1s 0 1s 2s 3s 4s - or in other words 20% of the time the true
υ -4s
mean is indicated by υ
mean will NOT lie between ±1.29s
4s -4s -3s -2s -1s 0 1s 2s 3s 4s -4s -3s -2s -1s 0 1s 2s 3s 4s

mean is indicated by υ

SIGNIFICANCE TESTS The ‘t Test’ (Student t-

t-test)
• Tests whether the difference between two Has two uses:
results is significant (or merely due to random (1) Comparison of true value, µ and mean,
GNIFICANCE
variations)
TESTS The ‘t Test’ (Student
to detect t-test)
t-
if difference is significant
- used to decide whether the Week   2   between
difference 32  
- Used to detect the existence of systematic
the measured
er the difference between two and known values can be Has two uses: error or bias
explained by random errors - Calculate t (generally for 95% confidence level)
nificant (or merely due to random
 Significant  tests    
•  Approach  tests  whether  the  difference  between  the  two  results  is  significant  (due  to  
systema,c  error)  or  not  significant  (merely  due  to  random  error).  

Null  hypothesis,  ho  

The  values  of  two  measured  quan,,es  do  not  differ  (significantly)  UNLESS  we  can  
prove  it  that  the  two  values  are  significantly  different.  
 
• The  calculated  value  of  a  parameter  from  the  equa,on  is  compared  to  the  
parameter  value  from  the  table.  
 
• If  the  calculated  value  is  smaller  than  the  table  value,  the  hypothesis  is  
accepted  and  vice-­‐versa.    
 

Week  2   33  
- or in other words 20% of the time the true
mean will NOT lie between ±1.29s

t-­‐test  
The ‘t Test’ (Student t-
t-test)
(2) Comparison of means ( ) of two samples
Has two uses:
- eg Compare mean of new method with a
(1) Comparison of true value, µ and mean, reference (or standard) method
to detect if difference is significant
- Accept Null hypothesis (Ho) if NO significant
- Used to detect the existence of systematic difference between methods ie the results are
error or bias the same, or =0
- Calculate t (generally for 95% confidence level) - Calculate t, if tcalc < ttable, accept Ho to show that
- If value of tcalculate < tcritical (ie tcalc < ttable), there is NO significant difference in results
ACCEPT the null hypothesis, thus Ho: µ = - Use pooled estimate of std dev,
- Accepting Ho means that there is NO s2={(n1-1)s12+ (n2-1)s22} / (n1+n2-2),
significant difference (or no systematic
error) at the 95% confidence level, but or
there is 5% probability that there is a
sgnificant difference

EXAMPLE 2: Determine if results differ significantly

Week  2   34  
EXAMPLE 1: Detection of Systematic Error (Bias)

Week  2   35  
EXAMPLE 2: Determine if results differ significantly

Week  2   36  
 F-­‐test  
àComparing  the  precision  of  two  measurements  
• Compare  standard  devia,ons  (ie  random  errors  of  2  data  sets)  
F-TABLE
• Is  there  any  significant  
The difference  
‘F Test’between  both  methods?  
• Compares Std dev (ie random errors of 2 data sets)
- One tailed test: test: test whether method A is more
precise than method B (assumes A is always precise)
- Two tailed test: test: test whether methods A and B
differ in their precision (ie any method can be precise)
- F is ratio of two 2
nominator  
sample variances: ν1 s
F= = 1

ν2 s 22 denominator  
Ho: Population variances are equal (or ≅ 1)
[F is always >1, thus the smaller ν ie the
more precise is always the denominator]
If Fcalc < Ftable (Accept Ho) which means that there
is NO significant difference in precision between
the two methods

Week  2   37  
 Example Question: ONE ONE--TAILED F TEST
A proposed method for COD of wastewater was
compared with a standardized method
The results are given as follows:
Standardized method (8 (8 determinations):
determinations):
mean =72 mg/L, s = 3.31 mg/L
Proposed method (9 (9 determinations):
determinations):
mean = 72 mg/L, s = 1.51 mg/L (↓)
Is the proposed method significantly more precise
than the standardized method?
F = (SStd)2/(SProp)2 = (3.31)2/(1.51)2 = 4.8
Data values: 8 for Std & 9 for proposed, thus from
the F-
F-table degrees of freedom (N (N--1) = 7numerator
and 8denominator, Fcrit = 3.50
Since Fcalc >Ftable , reject Ho. Thus there is a
significant difference bet the methods and the
proposed method is significantly more precise
Set as denominator

Week  2   38  
Example: Determination of CO using a ‘Standard
Procedure’ gave an s value of 0.21 ppm. The
method was modified twice giving s1 of 0.15 and s2
of 0.12 (both 9 degrees of freedom).
freedom). Are the modified
methods significantly more precise than the std?
Ho : s1 = sstd Ho: s2 = sstd
s2std 0.212 s 2std 0.21 2
F1 = 2 = 2
= 1.96 F2 = 2 = 2
= 3.06
s1 0.15 s2 0.12
In standard methods the # of data is large, thus
s→σ,
→σ, & degrees of freedom becomes infinity, ∞
From F- num=∞, den=9; Fcrit = 2.71
F-table, num=∞
F1< Ftable : accept Ho but F2>Ftable : reject Ho
Only the 2nd modified method is is significantly
more precise than the standard method

Week  2   39  
F-­‐table  

Week  2   40  
 The Q TEST or DIXON’S TEST
(Detection of gross errors)

‘The Q-
Q-Test is used for detecting outlier (suspected
unreasonable data) which statistically does not
belong to the set’
Example:: 10.05, 10.10, 10.15, 10.05, 10.45, 10.10
Example
• By inspection,
inspection, 10.45 seems to be out of the data
normal range (More easily observed when numbers are
arranged in a decreasing or increasing order)
10.05, 10.05, 10.10, 10.10, 10.15, 10.45
• Can/should this data be eliminated … ? (The mean
will change from the original value if changed!)

Contd…
Week  2   41  
 Use this
Equation:

The Qcal is compared with the Qtable and the null

hypothesis, HoHo is checked
10.45 - 10.15
Q expt = = 0.75
10.45 - 10.05
From Q-
Q-table (@95% & N=6) Q = 0.625
(Q-table:Next slide )
Qcal > Qtable ∴ data (10.45) can be rejected

Week  2   42  
 Q TABLE
No. of Observations Confidence Level
90% 95% 99%
3 0.941 0.970 0.994
4 0.765 0.829 0.926
5 0.642 0.710 0.821
6 0.560 0.625 0.740
7 0.507 0.568 0.680
8 0.468 0.526 0.634
9 0.437 0.493 0.599
10 0.412 0.466 0.568

Week  2   43  
 EXAMPLE QUESTION: Q-
Q-TEST

The following data was obtained for the

determination of nitrite concentration (mg/L)
in a sample of river water:
0.403, 0.410, 0.401, 0.380, 0.400, 0.413, 0.411
Should the data 0.380 be retained?

Q = |0.380 - 0.400|/|0.413 - 0.380)| = 0.606

Q-table: Sample size 7, Qtable = 0.570
From the Q-
Qcalc>Qtable, thus the suspect outlier is rejected

Week  2   44  
 Example:  
An  analysis  on  calcite  gave  the  following  percentage  of  CaO:    
55.45,  56.04,  56.23,  56.00,  55.08  
  Q:  Is  there  any  that  data  should  be  
rejected  at  95%  confidence  level?  
Solu2on:    
• Arrange  data  
55.08,  55.45,  56.00,  56.04,  56.08,  56.23  
• Suspected  data:   55.45  OR  56.23  
Qtable  from  5  determina2ons,  95%  =  0.710  
56.23 - 56.08
Q calc =
56.23 - 55.45 Qcalc<Qtable.  Data  cannot  be  rejected.  
= 0.19

55.45 - 56.00
Q calc = Qcalc  =  Qtable.  Data  cannot  be  rejected.    
56.23 - 55.45
= 0.71

Week  2   45