Population
N, ,
Sample
n, x, s
x1,x2, ... xn
sample mean ( x ); the mean of a limited sample drawn from a population of data
x 1 + x 2 + + x n
n
x = xi n =
i =1
(x i )2 N
s=
i =1
(x i x )2
(n 1)
i =1
Degrees of freedom: n 1
xn can be calculate from (n 1 ) data points and x .
Ex
x = 7 + 18 + 10 + 15 = 12.5
4
s=
Range
(7, 18, 10, 15)
18 7 = 11
Replicate Data on the Calibration of a 10-ml Pipet
Trial
Vol, mL
Trial
Vol, mL
Trial
Vol, mL
Trial
Vol, mL
Trial
Vol, mL
1
2
3
4
5
6
7
8
9
10
9.988
9.973
9.986
9.980
9.975
9.982
9.986
9.982
9.981
9.990
11
12
13
14
15
16
17
18
19
20
9.980
9.989
9.978
9.971
9.982
9.983
9.988
9.975
9.980
9.994
21
22
23
24
25
26
27
28
29
30
9.992
9.984
9.981
9.987
9.978
9.983
9.982
9.991
9.981
9.969
31
32
33
34
35
36
37
38
39
40
9.985
9.977
9.976
9.983
9.976
9.990
9.988
9.971
9.986
9.978
41
42
43
44
45
46
47
48
49
50
9.986
9.982
9.977
9.977
9.986
9.978
9.983
9.980
9.983
9.979
x = 9.982 mL
s = 0.0060
4-1
Exercise
Calculate 10 s using n.
Calculate 10 ss using n 1.
Mean of s using n 1
10 x 5 measurements
0.0053
0.0059
5 x 10 measurements
0.0058
0.0061
2 x 25 measurements
0.0059
0.0061
1 x 50 measurements
0.0060
0.0060
y=
( x )2
1
exp
2
2
x
, dz = dx)
Normal Error Curve (z =
ydx =
1
e
2
( ydx = 1)
z 2
2 dz
Max at z = 0, Symmetric
0.399
0.4
Decaying exponentially
Probability; Area under the curve
0.3
Range
1
2
3
inflection
point
0.242
Probability (Area)
68.3%
95.5%
97.7%
0.2
w1/2 = 2.354
0.1
4-2 Students t
0.0
"Student"
W. S. Gossett (1908)
0
w=4
Confidence Intervals
confidence level (%)
Confidence interval of :
=x
ts
n
4-2
Tab 4-2
Values of Students t
Confidence Level
degrees of freedom
1
2
3
4
5
Ex
50%
90%
1.000
0.816
0.765
0.741
0.727
0.674
6.314
2.920
2.353
2.132
2.015
1.645
95%
98%
99%
12.706
4.303
3.182
2.776
2.571
1.960
31.812
6.965
4.541
3.747
3.365
2.326
63.657
9.925
5.841
4.604
4.032
2.576
99.5%
99.9%
127.32 636.619
14.089 31.598
7.453 12.924
5.598
8.610
4.773
6.869
2.807
3.291
s = 0.40
degrees of freedom = n 1 = 4
(50%) = x
ts
(0.741) 0.40
= 12.54 0.13
= 12.54
n
5
(90%) = x
ts
(2.132) 0.40
= 12.54 0.38
= 12.54
n
5
Values of t
n
Tab
degrees of freedom
1
2
3
4
5
Confidence Level
50%
0.707
0.471
0.382
0.331
0.297
90%
4.465
1.686
1.176
0.953
0.823
95%
98%
99%
99.5%
99.9%
8.984
2.484
1.591
1.241
1.050
22.494
4.021
2.270
1.676
1.374
45.012
5.730
2.920
2.059
1.646
90.029
8.134
3.726
2.504
1.949
450.158
18.243
6.462
3.851
2.804
0.0320
0.0325
4-3
0.0330
x1 x 2
spooled
n1n2
n1 + n2
(x i x1)
set 1
spooled =
(x 2 x 2 )
set 2
n1 + n2 2
degrees of freedom = n1 + n2 2
Ex
x = 2.310109 g, s = 0.000143 g, n1 = 7
from dry air by removing O2: Cu(s) +
1 O (g)
2 2
CuO(s)
x = 2.299472 g, s = 0.001379 g, n2 = 8
from decomposition of N2O
spooled =
tcal =
0.0001432 (7 1) + 0.0013792 (8 1)
= 0.001017
7+82
2.310109 2.299472
0.001017
7 8 = 20.2
7+8
degrees of freedom = 7 + 8 2 = 13
ttab(99.9%) < 4.587 << 20.2
Q=
Gap
Range
Gap = 0.11
12.47 12.48
12.53
12.56
12.67
Range = 0.20
Tab 4-4 Q for rejection
Qrej(90% confidence)
4
5
6
7
8
0.76
0.64
0.56
0.51
0.47
4-4
(xi,yi)
di
y = mx + b
di = yi (mxi + b)
Seek to minimize the squares of the deviations (variance).
2
m d i = 0 m x i 2 + b x i = x i y i
2
m x i + nb = y i
di = 0
b
xi yi xi
n
yi
Solution: Cramers Rule m =
, b=
xi 2 xi
xi n
m=
n (x i y i ) x i y i
b=
where D = n
(x i )2 ( x i )
xi 2 xi yi
xi yi
xi 2 xi
xi n
(x i 2 ) y i (x i y i ) x i
D
m
n x i y i x i y i nx k x i
=
=
y k y k
D
D
2
y2 2 2
m
m
2
2
=
yk y
= 2 n x k 2nx k
y k
y k
D k
k
k
y2 2
= 2 n x k 2 2n x i x k + n
D
i
k
2
n y
=
D
y 2 xi 2
Similarly, b 2 =
D
(d i d )
where y s y =
( x i )
( x i ) + ( x i )2
y2 2
2
= 2 n x i n
di 2
( x i )2
n2
degrees of freedom
*2 degrees of freedom were used up in determining m and b.
m = y
n
D
b = y
(x i 2 )
D
4-5
(d i 2 )
n2
(x i x ) ( y i y )
(x i x )2 (y i y )2
r=
r = 0
no correlation
r = 1 complete correlation
Tab 4-5
2
xi
yi
xi yi
xi
1
3
4
6
2
3
4
5
2
9
16
30
1
9
16
36
14
14
57
62
y = mx + b
D = 462 14 = 52
m=
4 57 14 14
= 0.61538
52
b=
62 14 57 14
= 1.34615
52
d i 2 = 0.076923
y = 0.19612
r=
m = y
(x i x ) ( y i y )
(x i x )2 (y i y )2
n
= 0.054394
D
b = y
xi 2
D
= 0.21415
8
= 0.9923
13 5
Absorbance
reagent
0
0.099
0.099
0.100
0.185
0.187
0.188
standard
10
0.282
0.272
0.272
solutions
15
0.392
0.345
0.347
20
0.425
0.425
0.430
25
0.483
0.488
0.496
blank
4-6
0.5
out of
the linear range
0.4
absorbance
of
unknown
0.3
0.2
linear range
0.1
0.0
10
15
m = 0.01630
b = 0.1040
m = 0.00022
b = 0.0026
20
25
y = 0.0059
x=
y y b b
m m
y 2 1 x 2n x i 2 2x x i
=
+
D
D
D
m 2 k
k; # of y-measurements
For y = 0.373,
4-7