26 - STANDARD ADDITIONS

SDSU CHEM 251

 STANDARD ADDITION
• The standard addition process is a way of getting around complications
due to the sample matrix negatively impacting results.
2+
• The sample (e.g. Pb ) is prepare (it may be diluted) and then a known
2+
amount of standard (Pb ) is added to the sample.

• Measurements are compared for the sample with and without the
added standard to determine the concentration of the analyte in the
sample.

• As long as the amount of standard solution added to the sample is

relatively small the sample does not need to be prepared in a
comparable matrix, as the dilution should be minimal.
 STANDARD ADDITIONS
• Standard addition - the addition of a known amount of
standard to the sample - can minimize the matrix effects.

• Single standard addition can be performed in two ways:

• Twosolutions with equal amounts of sample, one with a

known amount of standard.

• One solution of sample, measured before and after the

addition of a known amount of standard.

• Thesignals from each solution can be used to extrapolate the

concentration of the sample in the solution.
 SINGLE ADDITION - TWO FLASKS
A 1.00 mL sample of blood is diluted to volume add Vo of CA add Vstd of Cstd

in a 5.00 mL volumetric flask. When measured

for it’s Pb2+ content the signal (Ssamp) was 0.193.
A second 1.00 mL blood sample was prepared
and spiked with 1.00 µL of 1560 ppb Pb2+ dilute to Vf

before being diluted to 5.00 mL. When the

spiked sample was measured the signal (Sspike)
was determined to be 0.419. What is the
concentration of Pb2+ in the blood sample? V V V
Ssamp Sspike
VO : volume of sample VO = 1.00mL =
V V
Vspike : volume of spike solution CA O CA VO + Cspike spike
Vspike = 1.00 µL = 1.00 ×10 −3 mL VF VF VF
VF : final solution volume
VF = 5.00mL
0.193 0.419
Cspike = 1560 ppb =
VO ! V V $ 1.00mL 1.00mL 1.00 ×10 −3 mL
Ssamp = kACA Sspike = kA # CA O + Cspike spike & CA CA +1560
VF " VF VF % Ssamp = 0.193 5.00mL 5.00mL 5.00mL
Ssamp Sspike
V
=
V
Sspike = 0.419 0.193 0.419
CA O CA VO + Cspike spike = CA = 1.33ppb
VF VF VF CA = ? 0.200CA 0.200CA + 0.3120 ppb
 STANDARD ADDITION - ONE FLASK
A 5.00 mL blood sample is measured for add Vstd of Cstd

it’s concentration of Pb2+, the resulting

signal (Ssamp) is found to be 0.712.
Vo Vo

To the 5.00 mL blood sample, 5.00 µL of a Vo Vstd

Pb2+ standard (1560 ppb)is added. When
Concentration CA CA C std
of Analyte Vo Vstd Vo Vstd

the blood sample is remeasured the signal

(Sspike) is now 1.546. What is the
concentration of Pb2+ in the blood sample?
0.712 1.546
=
Ssamp = kACA VO = 5.00mL CA 5.00mL # 5.00 ×10 −3 mL &
CA +1560 ppb % (
Vspike = 5.00 µL = 5.00 ×10 −3 mL 5.005mL $ 5.005mL '
! VO Vspike $
Sspike = kA ## CA + Cspike && VF = 5.005mL
" VO +Vspike VO +Vspike % 0.712 1.546
Cspike = 1560 ppb = CA = 1.33ppb
Ssamp Sspike CA 0.9990CA +1.558ppb
= Ssamp = 0.712
CA VO Vspike
CA + Cspike Sspike = 1.546
VO +Vspike VO +Vspike
CA = ?
 STANDARD ADDITION
• Multiplestandard additions:
where a known amount of sample
is added to multiple flasks, with
varied amounts of standard (e.g.
iron UV analysis lab).

• Though a very effective means of

doing a calibration it is often not
used due to the fact that each new
sample must be analyzed with it’s
own set of standard additions.