ANÁLISIS DE LA INCERTIDUMBRE EN

RESULTADOS CUANTITATIVOS

Joel Reza González

Instituto Mexicano del Petróleo

Área de Investigación en Termofísica
 PROGRAMA DEL CURSO-TALLER

5. MÉTODOS DE CALIBRACIÓN EN ANÁLISIS INSTRUMENTAL.

5.1 Gráficas de calibración en análisis instrumental

5.2 La recta de regresión de y sobre x
5.3 Errores en la pendiente y ordenada en el origen de la recta de regresión
5.4 Cálculo de una concentración y su error aleatorio
5.5 Límites de detección y cuantificación

6. PROPAGACIÓN DE ERRORES ALEATORIOS

 Propagation of uncertainties

Most physical quantities usually cannot be measured in a single direct measurement,

but are instead found in two distinct steps. First, one measures one or more quantities
x, y,…, that can be measured directly and from which the quantity of interest can be
calculated. Second, using the measured values of x, y,… , one calculates the quantity
of interest itself. For example, to find the area of a rectangle, one actually measures
its length l and height h, and then calculates its area A as A = lh.

When a measurement involves these two steps, the estimation of uncertainties also
involves two steps. One must first estimate the uncertainties in the quantities that are
measured directly, and then find out how these uncertainties “propagate” through the
calculations to produce the uncertainty in the final answer.
   q  2  q 
2

q    x   ...   z  

  x   z  
 Uncertainty in sums and differences

Suppose that several quantities x,.. ,w are measured with uncertainties x,...,w, and the
measured values used to compute

q  x  ...  z  (u  ...  w)

If the cuadratic uncertainties in x,...,w are know to be independent and random, then the
uncertainty in q is the quadratic sum of the original uncertainties.

q  (x) 2
 ...  (z ) 2  (u ) 2  ...  (w) 2 

In any case, q is never larger than their ordinary sum,

q  x  ...  z  u  ...  w
Un experimentador mezcla dos muestras líquidas contenidas en recipientes
separados (pesando por separado ambos recipientes, tanto llenos como
vacíos), y desea calcular la masa total del líquido.

M1 =Masa del recipiente 1 lleno = 540  10 g

m1 = Masa del recipiente 1 vacío = 72  1 g
M2 =Masa del recipiente 2 lleno = 940  20 g
m2 =Masa del recipiente 2 vacío = 97  1 g

Líquido 1
M = (M1 - m1) +( M2 - m2)
Líquido 2

¿Cuál es el valor de dicha masa así como de su incertidumbre asociada?

Un experimentador mezcla dos muestras líquidas contenidas en recientes
separados (pesando por separado ambos recipientes, tanto llenos como
vacíos), y desea calcular la masa total del líquido.

M1 =Masa del recipiente 1 lleno = 540  10 g

m1 = Masa del recipiente 1 vacío = 72  1 g
M2 =Masa del recipiente 2 lleno = 940  20 g
m2 =Masa del recipiente 2 vacío = 97  1 g

M = M1 - m1 + M2 - m2

M = 540 - 72 + 940 - 97 =1311 g

q  (10) 2
 (1) 2  (20) 2  (1) 2   22.4 g

El valor final, apropiadamente redondeado, es:

M = (1310  20) g
 Uncertainty in products and quotients

Suppose that x,...,w are measured with uncertainties x,...,w, and the measured values used
to compute
x  ... z
q
u  ... w
If the uncertainties in x,...,w are know to be independent and random, then the fractional
uncertainty in q is the quadratic sum of the original fractional uncertainties.

q   x  2  z 
2
 u 
2
 w 
2


    ...        ...    
q  x   z u   w  


In any case, it is never larger than their ordinary sum,

q x z u w
  ...    ... 
q x z u w
If, for example, we have the following measurements for m and v.

m = ( 0.53  0.01) kg v = (9.1  0.3) m.seg-1

To compute the best estimate for p = mv , as well as its uncertainty

 m = ( 0.53  0.01) kg v = (9.1  0.3) m.s-1

Then the best estimate for p = mv is

pbest = mbestvbest = (0.53) x (9.1) = 4.82 kg.m.s-1

To compute the uncertainty in p, we would first compute the fractional errors

m 0.01  v 0.3
  0.0189  1.89%   0.0330  3.30 %
mbest 0.53 vbest 9.1

The fractional uncertainty in p is then:

q
q
 1.89   3.30  
2 2
= 3.80 %

The absolute uncertainty in p is: p = 0.0380 x 4.82 = 0.1833 kg.m.s-1

value of p = (4.82  0.18) kg.m.s-1

Ver Ejemplo 16
 Uncertainty in a power

If the quantity x, is measured with uncertainty x, and the measured values used to compute
the power

q  xn

then the fractional uncertainty in q is n times that in x.

q x
n
q x
A student measures the aceleration of gravity g, by measuring the
time t for a stone to fall from a high h above the ground. After
making several timings he concludes that:

t = 1.6  0.1 s, and he measures the high h as h = 46.2  0.3 ft

By making use of h = 1/2gt2 he now calculates g as

2h
g 2
t

To determine g as well as the associated uncertainty

 t = 1.6  0.1 sec, and he measures the high h as h = 46.2  0.3 ft

By making use of h = 1/2gt2 he now calculates g as

2h 2  46.2 ft 2
g 2 g  36 .094 ft  s
t (1.6s) 2

The uncertainty in this answer can be found by using the rules just developed

h 0.3 t 0.1
  0.65 %   6.25 %
h 46.2 t 1.6

The factor 2 has no uncertainty. According with the rule in previous slide the fractional
uncertainty of t2 is twice that of t (2 x 6.25 =12.50 %). Therefore, applying the rule for
products and quotients we find the fractional uncertainty.

q
q
 0.65
2

 12 .50 2  12 .52 %
And hence the uncertainty g = (36.094 ft sec-2) x (12.52/100) = 4.52 ft sec-2..

Thus, the final answer, properly, rounded is:

g = 36  5 ft.sec-2
 Measured quantity times
exact number

If the quantity x, is measured with uncertainty x, and is used to compute the product

q  Bx

where B has no uncertainty, then the uncertainty in q is just |B| times that in x,

q  B x
 The thickness T of 100 sheets of paper is measeured, getting the result

T = 1.3  0.1 inches,

To determine the thickness t of a single sheet, as well as the asociated uncertainty

If the thickness T of 100 sheets of paper is measeured, getting the result

T = 1.3  0.1 inches,

Then, it immediately follows that the thickness t of a single sheet is

T  t *100

1
t T
100

= 0.013  0.001 inches.

 Uncertainty in any function of one
variable

Suppose that x is measured with uncertainty x and the measured values used to calculate
the function q(x), then the uncertainty q is

q
q  x
x

Ver Ejemplo 18
As a simple application of this rule, suppose that we have measured an angle  as.

 = 20  3 deg.

And that we wish to find cos , as well the associated uncertainty

 cos 
(cos )  

  = 20  3 deg.

We wish to find cos . Our best estimate of cos  is, of course, cos 20o = 0.94, and according
to the previous rule, the uncertainty is
 cos 
(cos )  

 (cos )   sin   (in rad )
It is indicated that  must be expressed in radians, because the derivative of cos is -sin
only if  is expressed in radians. Therefore we rewrite  = 3o as  = 0.05 rad. Thus,

(cos) =(sin 20o) x 0.05 = 0.34 x 0.05 = 0.02

Thus the final answer is

cos  = 0.94  0.02

 Uncertainty
Uncertaintyininproducts
a function
andofquotients
several
variables

Suppose that x,...,z are measured with uncertainties x,...,z, and the measured values used to
compute the function q(x,...z). If the uncertainties in x,...z are independent and random, then
the uncertainty in q is
  q  2  q 
2

q    x   ...   z  
  x   z  


In any case, it is never larger than their ordinary sum

q q
q  x  ...  z
x z
 OBJECTIVE

Análisis de errores en
parámetros experimentales y
calculados
Determinación de la solubilidad en
agua de compuestos orgánicos
 Alícuota
Col. Gen.

Disolución madre Dilución con

del EI en 1-octanol 1-octanol

EXTRACCIÓN
Análisis cuantitativo CON 1-OCTANOL

Disoln.
Ac.
180 o

Solubilidad en
agua del soluto Reposo Agitación
de interés
 Madre n-hexano
0.0305 g disoln.
0.32%
0.0268 g n-hexano 8.2392 g octanol 9.9E-5 g n-hexano 8.2542 octanol
(0.37%) (1.2E-3%) (0.43%) (1.2E-3%)

8.1215 g disoln.
(1.2E-3%)
1.11E-4 g n-heptano 50.6936 g
(1.20 %) (1.9E-4%)
(error de dilusiones
+ análisis Análisis
cromatográf ico) cromatográf ico
f ase orgánica 1.2E-4 g n-hexano/10 g disoln.
(0.43%)

Solubilidad de 50.6936 g (1.9E-4%)

disoln. acuosa de col.
n-heptano en agua: generadora
Sw = 2.18 ± 0.03 mg/L
Sw = 2.18 ± 1.20 % mg/L
 DGsol,i, DHsol,i, DSsol,i
Disolución
Sólido Acuosa
DGsub,i
DHsub,i

DSsub,i
DGf,i DGsv,i
DHf,i DSs,i DHsv,i
DSf,i DHs,i DSsv,i

DGs,i

DGv,i, DHv,i, DSv,i

Líquido
(Subenfriado) Vapor

Ciclo termodinánico para el proceso de disolución en agua de una sustancia sólida. Se ilustran las
contribuciones termodinámicas de la vaporización, la solvatación, la disolución del soluto líquido
puro (subenfriado), la sublimación y la disolución del soluto sólido. Los estados estándar son dilución
infinita para la disolución acuosa, la fase gas ideal a 1 atmósfera, para la fase vapor y el sólido o
líquido puro (subenfriado) a 1 atmósfera y 298 K (Privalov y Gill, 1988; Zhang y Gobas, 1995;
Ogawa et al., 1997).
 Solución Fusión

DG s ,i   RT ln xi  DG f ,i DG f ,i  DH f ,i  TDS f ,i

  ln xi  Tm
DH f ,i DH f ,i (Tm )   DC p dT
DH s ,i  R   DH f ,i
  (1 / T )  p
T

DH f ,i (Tm ) Tm DC p
DH s,i  DGs,i DS f ,i   dT
DS s,i  Tm T T
T

Vaporización Solvatación

DG v ,i   RT ln pi ( s )  DG f ,i DG sv ,i  DGs ,i  DGv ,i

  ln pi ( s)  DH sv ,i DH s ,i  DH v ,i
DH v,i  R   DH f ,i
  (1 / T ) p
DS sv ,i  DS s ,i  DS v ,i
DH v,i  DGv,i
DS v,i 
T
 CASO DEL PIRENO

Parámetro Incertidumbre Referencia


xi (4.39  0.10) x 10-9  2.30 % 1
T (297.76  0.03) / K  0.01 % 1
Tm (488.97  0.01) / K  0.002 % 2
DHf, i(Tm) (29.372  0.050) / kJ mol-1  0.17 % 2
as = -24.6 3.5 14.23%
bs = 0.7857 0.0094 1.20%
2
 
al = 134.2 16.5 12.30%
bl = 0.467 0.033 7.07%
pi (6.0  0.2) x 10-4 Pa  3.33 % 3

Solubilidad en agua a 297.76 K, expresada en fracción molar. 1 Reza et al. (2002), 2 Goursot et al. (1971) R =
8.3145 J mol-1 K-1
 CASO DEL PIRENO
PROCESO DE FUSIÓN

CP(s) = aS + bST

CP(l) = al + blT

DH f , i  DH f , i (Tm )  aS  al Tm  T  

bS  bl  T 2  T 2 
m
2

DH f , i (Tm ) T 
DS f , i   aS  al ln m   bS  bl Tm  T 
Tm T 
CASO DEL PIRENO

Parámetro Incertidumbre

aS = -60.20  18.83  31.28 %

bS = 0.970  0.017  1.80 %
al = 109.8  25.77  23.47 %
bl = 0.564  0.051  9.06 %
 CASO DEL PIRENO

Incertidumbre
Parámetro
porcentual
DHf, i (14.42  8.66) kJ mol-1  60.04 %
DSf, i (32.18  24.08) J mol-1 K-1  74.85 %
TDSf, i (9.59  7.17) kJ mol-1  74.86 %
 CASO DEL PIRENO

Proceso de solución Proceso de vaporización

DHS, i, (27.69  10.08) kJ mol-1 DHv, i, (76.73  11.71) kJ mol-1

DSS, i, -(0.0429  0.0867) kJ mol-1 K-1 DSv, i, (0.1167  0.0930) kJ mol-1 K-1
-TDSS, i, (12.79  25.85) kJ mol-1 -TDSv, i, -(34.80  27.72) kJ mol-1
DGS, i, (40.48  15.90) kJ mol-1 DGv,i, (41.93  15.97) kJ mol-1

Proceso de solvatación

DHsv, i, -(49.04 21.77) kJ mol-1

DSsv, i, -(0.0159  0.0178) kJ mol-1 K-1
-TDSsv, i, (47.59  53.31) kJ mol-1
DGsv, i. -(1.45  3.19) kJ mol-1
 Ecuación básica para predecir la fracción molar de
saturación de un sólido en un líquido (Sandler, et al., 1999):

D H f ,i (Tm )  T  1 Tm 1 Tm DC p
ln 1 x1   1    
T
DC p dT  T dT
RT  Tm  RT R T

bS  bl  T 2  T 2 
 C (s)  C (l )dT  a S  al Tm  T  
Tm
p p m
T 2

Tm C p (s)  C p (l )dT  a T 

 al ln  m   bS  bl  Tm  T 

T T
S
T 

Ver Ejemplo 17
Fluid Phase Equilibria, 2003
 Análisis de extraibles en freón 113, presentes en
muestras de sedimento Istmo, despues de su extracción
con CO2 supercrítico

1.4
1.2 y = 0.003206x + 0.035283 a = 0.035 ± 0.039
R = 0.9993
1
Absorbancia

b = 0.00321 ± 0.00014
0.8 = 0.00321 ± 4.39 %
0.6

0.4

0.2

0
40 140 240 340 440
Concentración / ppm-masa
 Análisis de extraibles en freón 113, presentes en
muestras de sedimento Istmo, despues de su extracción
con CO2 supercrítico

Muestra 1 (20106  1331) mg extraibles/kg matriz sólida

 6.62 %
Muestra 2 (17896  950) mg extraibles/kg matriz sólida
 5.30 %
Muestra 3 (19987  1071) mg extraibles/kg matriz sólida
 5.36 %
Error Promedio de las tres mediciones = 5.76 %

Promedio = 19330 mg/Kg

Desv. Est. = 1243 mg/Kg

s
DER  100  6.43%
x
s 1243
t  4.3  3086 ppmw  15.96%
n 3
D. Jaques. Error analysis of isobaric liquid-vapor equilibrium data
for mixed solvents containing salts at saturation. In
Thermodynamic behavior of electrolytes in mixed solvents-II W. F.
Furter (ed.) Advances in Chemistry Series 177, Chapter 4.
American Chemical Society, Washington D.C. 1976
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