Electroplating
4
Titration
Applications
Brochure
General Titrators
Selected Titration Applications
For the Electroplating Industry
METTLER TOLEDO
Contents
Method Title
Electroless Copper Bath
M062
Electroless copper bath: Determination of Copper
M063
Electroless copper bath: Free Complexing agents
M064
Electroless copper bath: Sodium Hydroxide and Formaldehyde
Electroless Nickel Bath
M065
Electroless Nickel Bath: Determination of Sodium Hypophosphite
M066
Electroless Nickel Bath: Determination of Nickel
M067
Electroless Nickel Bath: Determination of Sodium Orthophosphite
METTLER TOLEDO
Electroplating Industry
METTLER TOLEDO
Application M062
Electroless Copper Bath: Determination of Copper
Method for determination of copper in electroless copper bath by iodometric titration.
Sample
Compound
Electroless copper bath,10 mL
(see “Preparation”)
2+
Copper (Cu ),
M = 63.54 g/mol, z = 1,
Copper Sulfate (CuSO4),
M= 159.60 g/mol, z = 1,
Copper Sulfate Pentahydrate
(CuSO4.5H2O),
M = 249.68 g/mol, z = 1
Chemicals
25% Sulfuric acid, 40 mL
10% Potassium iodide, KI, 5 mL
10% Potassium thiocyanate,
KSCN, 5 mL.
Titrant
Sodium thiosulfate, Na2S2O3
c(Na2S2O3) = 0.1 mol/L
Standard
Potassium iodate, KIO3
20-30 mg
Indication
DMi140-SC (Combined
platinum ring redox electrode)
Chemistry
2CuSO4 + 4KI + → 2CuI +
2K2SO4 + I2
2Na2S2O3 + I2 → Na2S4O6 +
2NaI
Preparation and Procedures
CAUTION
‐ Use safety goggles, a lab coat, wear mask and
gloves. Always work in a fume hood.
‐ Ensure cleaning of sensor after each titration.
Sample Preparation: Electroless copper bath
‐ Take 158 mL deionized water in 200 mL
volumetric flask add 2 mL Cu-bath Ginplate Cu
406-C with stirring.
‐ While stirring add 20mL Ginplate Cu 406-B and
20 mL Ginplate Cu 406-A.
(Literature: GINPLATE CU 406)
Sample titration:
‐ Dispense 10 mL of sample from additional
dosing unit to the titration beaker placed on
sample changer.
‐ Add 40 mL of 25% H2SO4 from peristaltic pump.
‐ Add 5 mL of 10% KI from additional dosing unit.
‐ Add 5 mL of 10% KSCN from additional dosing
unit.
‐ Wait for 5 minutes with stirring
‐ Titrate with 0.1mol/L Na2S2O3.
‐ After completion of each sample, sensor, stirrer
and titration tubes are rinsed by deionized water
by means of membrane pump.
‐ Sensor is cleaned with deionized water in
conditioning beaker placed on sample changer
after each sample.
Remarks
Calculation
R1 = Q*C/m, g/L
R2 = Q*C/m, g/L
R2 = Q*C/m, g/L
C=
Q=
m=
M=
z=
(Cu content)
(CuSO4)
(CuSO4•5H2O)
M/z
Titrant consumption in mmol.
mass of the sample in mL
Molar mass of sample in g.
Equivalent number of sample
Waste
disposal
Copper solutions : If necessary,
neutralize the solution before
final disposal as special waste
Author,
Version
Ruby Das, IMSG AnaChem,
Version 2.0,
Revised: C. De Caro, MSG AnaChem
METTLER TOLEDO
‐
‐
‐
The method parameters have been optimized
for the sample of this application. It may be
necessary to adapt the method to your specific
sample.
This method allows a fully automated analysis
procedure. This method can be easily modified
for manual operation. Select “Manual stand” in
the method function “Titration stand”
Purity of potassium iodate used is 99.5%.
Literature:
‐ Ginplate Cu 406, (www.growel.com/tds/796.pdf ),
a trademark of Grauer & Weil India Ltd, www.growel.com
‐ Mettler-Toledo Applications M062 and M009.
Page 1 of 4
Titration Application M062
Instruments
‐ Titration Excellence T70/T90
(Other Titrators: depending on instrument type, manual operation and method
changes are necessary)
TM
‐ Rondo 20 Sample Changer with PowerShower (MT-51108003)
‐ XP 205 Balance
Accessories
‐
‐
‐
‐
‐
‐
3 x Additional dosing unit (MT-51109030)
3 x 10 mL DV1010 glass burette (MT-51107501)
1 x 5 mL DV1005 glass burette (MT-51107500)
100 mL Polypropylene titration beakers (MT-00101974)
Peristaltic pump SP250 (MT-51108016)
®
LabX pro titration software
Results
Results
Method-ID
Sample
Cu
CuSO4
CuSO4.5H2O
Sample
Cu
CuSO4
CuSO4.5H2O
Sample
Cu
CuSO4
CuSO4.5H2
Sample
Cu
CuSO4
CuSO4.5H2O
Sample
Cu
CuSO4
CuSO4.5H2O
Sample
Cu
CuSO4
CuSO4.5H2O
Copper
10 mL
2.663
6.688
10.463
10 mL
2.663
6.689
10.464
10 mL
2.668
6.701
10.483
10 mL
2.668
6.702
10.485
10 mL
2.663
6.688
10.463
10 mL
2.664
6.692
10.469
Method-ID
R1
Samples
Mean
s
srel
Copper
Copper
6
2.665
0.002
0.093
g/L
g/L
%
R2
Samples
Mean
s
srel
CuSO4
6
6.693
0.007
0.097
g/L
g/L
%
R3
Samples
Mean
s
srel
CuSO4.5H2O
6
10.471
0.010
0.097
g/L
g/L
%
(1/6)
g/L
g/L
g/L
(2/6)
g/L
g/L
g/L
(3/6)
g/L
g/L
g/L
(4/6)
g/L
g/L
g/L
(5/6)
g/L
g/L
g/L
(6/6)
g/L
g/L
g/L
Statistics
Titration curve
METTLER TOLEDO
Page 2 of 4
Titration Application M062
Table of measured values
Volume
mL
Increment
mL
0.0000
1.0000
1.1000
1.2000
1.3000
1.4000
1.5000
1.6000
1.7000
1.8000
1.9000
2.0000
2.1000
2.2000
2.3000
--------3.8000
3.9000
4.0000
4.1000
4.169456
4.2000
4.3000
4.4000
4.5000
4.6000
4.7000
4.8000
4.9000
5.0000
5.1000
EQP1
Signal
mV
NaN
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
----------------0.1000
0.1000
0.1000
0.1000
NaN
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
351.1
348.3
347.3
347.0
346.6
346.3
345.8
345.3
344.6
343.9
343.1
342.4
341.8
341.1
340.4
---------320.0
316.5
311.1
301.5
279.8
270.3
255.3
248.4
243.5
240.1
237.1
234.4
232.0
230.0
228.1
Change
mV
NaN
-2.8
-1.0
-0.3
-0.4
-0.3
-0.5
-0.5
-0.7
-0.7
-0.8
-0.7
-0.6
-0.7
-0.7
------------2.8
-3.5
-5.4
-9.6
NaN
-31.2
-15.2
-6.9
-4.9
-3.4
-3.0
-2.7
-2.4
-2.0
-1.9
1st deriv.
mV/mL
Time
s
NaN
NaN
NaN
NaN
NaN
-4.94
-4.69
-6.07
-6.78
-7.19
-7.18
-7.00
-6.79
-6.78
-7.02
---------------33.46
-76.65
-122.03
-153.00
-159.19
-158.95
-138.10
-97.40
-52.08
-21.68
NaN
NaN
NaN
NaN
NaN
0
4
7
10
13
16
19
22
25
28
31
34
37
40
43
-------89
92
96
104
NaN
122
130
134
139
142
145
148
151
154
157
Temperature
°C
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
-----------------------25.0
25.0
25.0
25.0
NaN
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
Comments
• Be careful! If cyanide is present in the sample the addition of a sulfuric acid solution must be
performed in a ventilated fume hood (formation of poisonous HCN!).
• This electroless copper bath is used for chemical copper deposition on printed circuit boards. It
consists of sodium hydroxide, formaldehyde, weakly complexed copper, free complexing agent(s), and
additives.
• Titer determination of 0.1 mol/L Na2S2O3 is done as per the Mettler-Toledo application M009 and
mean value found is 1.00509. The mean value of the titer is automatically stored as part of the setup
by the function TITER.
Principle :
‐ A weaker copper complex is decomposed at room temperature by the acid medium. A stronger
complex is decomposed in the same way at elevated temperature.
‐ After decomposition the sample is cooled at room temperature.
‐ Then potassium iodide (KI) and potassium thiocyanate (KSCN) are added.
‐ Cu(II) is reduced with excess iodide (I-) and subsequently precipitated as CuI in the presence of
thiocyanate (SCN ). KSCN is added to avoid adsorption of I2 on the surface of CuI :
2+
2Cu
+ 4I
-
→
2CuI + I2
‐
The amount of iodine formed is proportional to the Cu (II) content. Cover the beakers to avoid loss of
iodine. The complete reduction of Cu (II) requires 5 min.
‐
The liberated I2 is then titrated at room temperature with Na2S2O3.
2-
2 S2O3
‐
‐
+ I2
→
2-
S4O6
+ 2I
-
Stir moderately. Vigorous stirring causes loss of I2.
TM
Alternative: Photometric indication with DP5 Phototrode ; indicator : starch
METTLER TOLEDO
Page 3 of 4
Titration Application M062
Method
001 Title
Type
Compatible with
ID
Title
Author
......
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
General titration
T70/T90
Copper
Determination of copper
admin
Evaluation and recognition
Procedure
Standard
Threshold
100.0 mV/mL
Tendency
Negative
Ranges
0
Add. EQP criteria
No
Termination
At Vmax
10.0mL
At potential
No
At slope
No
After number of
recognized EQPs
Yes
Number of EQPs
1
Combined termination
criteria
No
Accompanying stating
Accompanying stating
No
Condition
Condition
No
1
Copper
Fixed volume
10.0 mL
1.0 g/mL
1.0
25.0°C
003 Titration stand (Rondo/TowerA)
Type
Rondo/TowerA
Titration stand
Rondo60/1A
Lid handling
No
004 Dispense (normal) [1]
Titrant
Concentration
Volume
Dosing rate
Condition
CU SAMPLE
1
10.0 mL
60.0 mL/min
No
005 Pump
Auxiliary reagent
Volume
Condition
H2SO4 25%
40.0 mL
No
006 Dispense (normal) [2]
Titrant
Concentration
Volume
Dosing rate
Condition
10% KI
1
5.0 mL
60.0 mL/min
No
007 Dispense (normal) [3]
Titrant
Concentration
Volume
Dosing rate
Condition
10% KSCN
0.1
5.0 mL
60.0 mL/min
No
011 Calculation R1
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
Cu
g/L
R1=Q*C/m
C=M/z
M[Copper]
z[Copper]
3
No
Yes
No
No
No
012 Calculation R2
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
CuSO4
g/L
R2=Q*C/m
C=M/z
M[Copper sulphate]
z[Copper sulphate]
3
No
Yes
No
No
No
008 Stir
Speed
Duration
Condition
009 Instruction
Instruction
Mode
Time interval
Print
LabX command
Condition
010 Titration (EQP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature acquisition
Stir
Speed
Predispense
Mode
Volume
Wait time
Control
Control
Titrant addition
dV
Mode
dE
dt
t (min)
t (max)
METTLER TOLEDO
40 %
10 s
No
1
Time interval
300 s
Yes
No
No
013 Calculation R3
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
Na2S2O3
0.1 mol/L
mV
DM140-SC
mV
No
CuSO4.5H2O
g/L
R3=Q*C/m
C=M/z
M[Copper sulphate
pentahydrate]
z[Copper sulphate
pentahydrate]
3
No
Yes
No
No
No
014 Rinse
Auxiliary reagent
Rinse cycles
Vol.per cycle
Position
Drain
Condition
WATER
1
10.0 mL
Current position
No
No
015 Conditioning
Type
Interval
Position
Time
Speed
Condition
Fix
1
Conditioning beaker
10s
30%
No
40 %
Volume
1.0 mL
0
User
Incremental
0.1 mL
Equilibrium controlled
0.5 mV
1.0 s
3.0 s
30.0 s
016 End of sample
Page 4 of 4
Titration Application M062
METTLER TOLEDO
Application M063
Electroless Copper Bath: Determination of Free Complexing Agents
Method for determination of free complexing agents in electroless copper bath.
Sample
Electroless copper bath, 5 mL
Preparation and Procedures
CAUTION
‐ Use safety goggles, a lab coat and wear gloves. If possible,
work in a fume hood.
Compound
‐
Free complexing agents
Ensure accurate cleaning of sensor is sufficient after each
titration.
Sample Preparation :
‐
Chemicals
Deionized water, 60 mL
Indicator: 0.2 g Murexide
trituration with NaCl (1:500).
Electroless copper bath: Take 158 mL deionized water in
200 mL volumetric flask add 2 mL Ginplate Cu 406-Cwith
stirring. While stirring add 20 mL Ginplate Cu 406-B and 20
mL Ginplate Cu 406-A. (Literature : Ginplate CU 406)
Sample titration
Titrant
Standard
Indication
Copper Sulfate, CuSO4
c(CuSO4) = 0.01 mol/L
Ethylenediaminetetraacetic acid
disodium,C10H14N2Na2O8 • 2H2O
c(EDTA- Na2) = 0.01 mol/L
TM
:
‐
Add 0.2 g murexide trituration with NaCl (1:500) in the
beaker placed on sample changer.
‐
Dispense 5 mL of sample from additional dosing unit .
‐
Add 60 mL of deionized water from additional dosing unit.
‐
The sample is enough alkaline, and therefore no pH buffer is
needed for the pH adjustment in the alkaline region
necessary for EDTA titration .
‐
Titrate with 0.01 mol/L CuSO4.
‐
After completion of each sample sensor, stirrer and titration
tubes are rinsed by deionized water by means of membrane
pump.
‐
Sensor is cleaned with deionized water in the conditioning
beaker placed on sample changer after each sample.
DP5 Phototrode (555 nm)
(violet to yellow color)
Remarks
Chemistry
2+
Cu
+ Agent → Cu-Agent
‐
2+
At equivalence point :
2+
-
Cu + Murexide
+
Cu-Murexide
Calculation
→
R = Q*C/m*d, mol/L
Q=
C=
d=
m=
Titrant consumption in mmol
1000
Density of sample in g/mL
Mass of sample in mL
Waste
disposal
Copper solutions: If necessary,
neutralize the solution before
final disposal as special waste.
Author,
Version
Ruby Das, IMSG AnaChem, V2.0
Revised: C. De Caro, MSG AnaChem
Prior to use , adjust the output signal of the DP5
TM
Phototrode to approx.. 1000 mV in deionized
water before starting titration (100%
transmission) by turning the small knob on the
housing.
‐ Rinsing and conditioning of the Phototrode is
crucial to achieve accurate and precise results.
‐ Avoid formation of bubbles during titration by low
speed rate of stirrer, as they disturb photometric
indication.
‐ This method allows a fully automated analysis
procedure. This method can be easily modified
for manual operation. Select “Manual stand” in
the method function “Titration stand”.
‐ Sample may be dispensed manually using a
pipette instead of using an additional dosing
unit.
Literature :
‐ Ginplate Cu 406, ( http://www.growel.com/tds/796.pdf), a
trademark of Grauer & Weil India Ltd, www.growel.com
METTLER TOLEDO
‐
Page 1 of 4
Mettler – Toledo Application M063
Titration Application M063
Instruments
‐ Titration Excellence T50/T70/T90
(Other Titrators: depending on instrument type, manual operation and method
changes are necessary)
‐ XP205 Balance (MT-1106024)
TM
‐ Rondo 20 with PowerShower (MT-51108003)
Accessories
‐
‐
‐
‐
‐
‐
2 x Additional dosing unit (MT-51109030)
1 x 20 mL DV1020 glass burette (MT-51107502)
1 x 10 mL DV1010 glass burette (MT-51107501)
1 x 5 mL DV 1005 glass burette (MT-51107500)
100 mL Propylene titration beakers (MT-00101974)
LabX® pro titration software
Results
All results
Method-ID
Sample
R1 (Free
Sample
R2 (Free
Sample
R3 (Free
Sample
R4 (Free
Sample
R5 (Free
Sample
R6 (Free
complexing
complexing
complexing
complexing
complexing
complexing
FCA
5 mL (1/6)
agents) 5.773
5 mL (2/6)
agents) 5.762
5 mL (3/6)
agents) 5.739
5 mL (4/6)
agents) 5.758
5 mL (5/6)
agents) 5.767
5 mL (6/6)
agents) 5.758
mmol/L
mmol/L
mmol/L
mmol/L
mmol/L
mmol/L
Statistics
Method-ID
R1
Samples
Mean
s
srel
FCA
Free complexing agents
6
5.760
0.012
0.201%
Titration curve
METTLER TOLEDO
Page 2 of 4
Titration Application M063
Table of measured values
EQP1
Volume
mL
0.0000
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.7000
0.8000
0.9000
1.0000
1.1000
1.2000
1.3000
1.4000
-----------2.5000
2.6000
2.7000
2.8000
2.884740
2.9000
3.0000
3.1000
3.2000
3.3000
3.4000
3.5000
3.6000
3.7000
3.8000
Increment
mL
NaN
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
------------------0.1000
0.1000
0.1000
0.1000
NaN
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
Signal
mV
142.1
141.9
141.8
141.4
141.3
141.2
141.0
140.8
140.6
140.4
140.2
139.9
139.7
139.5
139.5
--------146.8
152.0
166.6
191.1
219.7
224.8
255.4
275.4
285.5
292.6
297.6
299.7
300.5
301.8
302.4
Change
mV
NaN
-0.2
-0.1
-0.4
-0.1
-0.1
-0.2
-0.2
-0.2
-0.2
-0.2
-0.3
-0.2
-0.2
0.0
----------4.4
5.2
14.6
24.5
NaN
33.7
30.6
20.0
10.1
7.1
4.4
2.7
0.8
1.3
0.6
1st deriv.
mV/mL
NaN
NaN
NaN
NaN
NaN
-1.75
-1.70
-1.78
-2.16
-2.37
-2.20
-2.17
-2.02
-1.82
-1.20
--------------64.12
132.23
207.50
260.65
274.61
274.47
245.25
182.47
111.63
56.08
NaN
NaN
NaN
NaN
NaN
Time
s
0
3
6
9
12
15
18
21
24
27
30
34
37
40
43
-----78
83
87
92
NaN
98
105
111
118
124
129
134
137
140
143
Temperature
°C
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
----------25.0
25.0
25.0
25.0
NaN
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
Comments
Standardization of 0.01M CuSO4 :
‐ Take 5 mL of 0.01M EDTA in a titration beaker.
‐ Add 50 mL deionized water.
‐ Add 0.1 g murexide trituration with NaCl (1: 500) with stirring.
‐ Titrate with 0.01M CuSO4.
TM
‐ Sensor used: DP5 Phototrode (555nm). The color change observed is from pink to yellow.
‐ Titer determination of 0.01 mol/L CuSO4 is done and mean value found is 0.97902. The mean value of
the titer is automatically stored as part of the setup by the function TITER.
Sample titration:
‐ The copper bath is diluted and then titrated with 0.01M Cu(II) titrant. No pH buffer is added, the sample
is alkaline.
‐ It is recommended to use a murexide trituration with NaCl.(1:500). Add the indicator just before starting
analysis.
‐ Keep sample free of air bubbles during titration. Air bubbles and undissolved impurities affect the
photometric indication.
‐ Due to the steep signal change, an EQP titration with fixed increments is used. The low threshold
value allows for different amounts of indicator.
‐ Titration time: approx. 4 minutes. A fixed predispensing shortens the titration time
Principle :
‐ Free complexing agents are titrated with Cu(II) solution in alkaline solution:
2+
2+
Cu
+ Agent
→
Cu-Agent
‐ At the equivalence point (simplified):
2+
+
Cu
+ Murexide →
Cu-Murexide (violet to yellow)
METTLER TOLEDO
Page 3 of 4
Titration Application M063
Method
001 Title
Type
Compatible with
ID
Title
. . .
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
Entry
General titration
T50 / T70 / T90
FCA
Free complexing agents
1
Free complexing agents
Fixed volume
5.0 mL
1.0220 g/mL
1.0
25.0°C
Arbitrary
003 Titration stand (Rondo/TowerA)
Type
Rondo/TowerA
Titration stand
Rondo60/1A
Lid handling
No
004 Dispense (normal) [1]
Titrant
Concentration
Volume
Dosing rate
Condition
CU SAMPLE
1
5.0 mL
60.0 mL/min
No
005 Dispense (normal) [2]
Titrant
Concentration
Volume
Dosing rate
Condition
WATER
100
60.0 mL
60.0 mL/min
No
008 Calculation R1
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
Free complexing agents
mmol/L
R1= Q1*C/m*d
C=1000
M[None]
z[None]
3
No
Yes
No
No
No
009 Rinse
Auxillary reagent
Rinse cycles
Vol.per cycle
Position
Drain
Condition
WATER
1
10 mL
Current position
No
No
010 Condition
Type
Interval
Position
Time
Speed
Condition
Fix
1
Conditioning beaker
20 s
10 %
No
011 End of sample
006 Stir
Speed
Duration
Condition
007 Titration (EQP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Wait time
Control
Control
Titrant addition
dV
Mode
dE
dt
t (min)
t (max)
Evaluation and recognition
Procedure
Threshold
Tendency
Ranges
Add. EQP criteria
Termination
At Vmax
At potential
Potential
Termination tendency
At slope
After number of
recognized EQPs
Number of EQPs
Combined termination
criteria
Accompanying stating
Accompanying stating
Condition
Condition
METTLER TOLEDO
10%
120 s
No
CuSO4
0.01 mol/L
Phototrode
DP5
mV
No
10%
None
0 s
User
Incremental
0.1 mL
Equilibrium controlled
1.0 mV
2 s
3 s
30 s
Standard
100.0 mV/mL
Positive
0
No
30.0 mL
Yes
1000
None
No
Yes
1
No
No
No
Page 4 of 4
Titration Application M063
METTLER TOLEDO
Application M064
Electroless Copper Bath: Determination of Sodium Hydroxide and Formaldehyde Content
Method for determination of sodium hydroxide and formaldehyde content in electroless copper bath.
Sample
Electroless copper bath, 5 mL
Preparation and Procedures
CAUTION
‐ Use safety goggles, a lab coat and wear gloves. If possible,
work in a fume hood.
Compound
Chemicals
‐
Sodium Hydroxide (NaOH),
M = 40.00 g/moL, z = 1
Formaldehyde (HCHO),
M = 30.03 g/moL, z =1
Ensure accurate cleaning of sensor is sufficient after each
titration.
Sample Preparation :
‐
Deionized water, 50 mL,
1 mol/L Na2SO3 (pH = 10.5),
10 mL
Electroless copper bath: Take 158 mL deionized water in
200 mL volumetric flask add 2 mL Ginplate Cu 406-Cwith
stirring. While stirring add 20 mL Ginplate Cu 406-B and 20
mL Ginplate Cu 406-A. (Literature : Ginplate CU 406)
Sample titration
Titrant
Standard
Indication
Chemistry
Hydrochloric acid, HCl
c(HCl) = 0.1 mol/L
Tris (hydroxymethyl)
aminomethane, (THAM),
50-100 mg
DGi111-Sc
Combined pH glass electrode
HCl + NaOH → NaCl + H2O
HCHO + Na2SO3 + H2O →
CH2OH•SO3Na + NaOH
Dispense 5mL of sample from additional dosing unit in the
titration beaker placed on sample changer.
‐
Add 50 mL of deionized water from additional dosing unit.
‐
Titrate with 0.1 mol/L HCl till the endpoint (i.e. pH = 10.5).
‐
pH of Na2SO3 solution is first adjusted to 10.5 to avoid
complicated blank correction.
‐
Dispense 10 mL of 1.0 mol/L Na2SO3 (pH = 10.5) from
additional dosing unit with stirring.
‐
Titrate with 0.1mol/L HCl.
‐
After completion of each sample sensor, stirrer and titration
tubes are rinsed by deionized water by means of membrane
pump.
‐
Sensor is cleaned with deionized water in the conditioning
beaker placed on sample changer after each sample.
‐
The nominal concentration of sodium hydroxide (NaOH) is
given in the auxillary value H[Nominal value of NaOH].
‐
The nominal concentration of formaldehyde (HCHO) is given
in the auxillary value H[Nominal value of HCHO].
Remarks
‐
Calculation
Waste
disposal
Author,
Version
METTLER TOLEDO
:
‐
R1 = E, pH (Dil. sample)
R2 = Q*C/m*d, g/L (NaOH content)
R3 = H[Nominal value of NaOH] – (Q*C/m*d), g/L
(Correction for NaOH)
R4 = Q*C/m*d, g/L (Formaldehyde content)
R5 = H[Nominal value of formaldehyde] – (Q*C/m*d),
g/L (Correction for formaldehyde)
C = M/z
Q = Titrant consumption in mmol.
M = Molar mass of sample in g.
z = Equivalent number of sample z=1
d = density of sample in g/L.
m = mass of sample in mL
Copper solutions: If necessary,
neutralize the solution before
final disposal as special waste.
‐
‐
‐
The method parameters have been optimized for the sample
of this application. It may be necessary to adapt the method
to your specific sample.
This method allows a fully automated analysis procedure.
This method can be easily modified for manual operation.
Select “Manual stand” in the method function “Titration
stand”.
Purity of Tris (hydroxymethyl) aminomethane used is
100.00%.
Sample may be added manually using a pipette instead of
using an additional dosing unit.
Literature :
‐ Ginplate Cu 406, ( http://www.growel.com/tds/796.pdf), a
trademark of Grauer & Weil India Ltd, www.growel.com
‐
Mettler – Toledo Application M064 and M003
Ruby Das, IMSG AnaChem, V 2.0
Revised: C. De Caro, MSG AnaChem
Page 1 of 6
Titration Application M064
Instruments
‐ Titration Excellence T90
(Other Titrators: depending on instrument type, manual operation and method
changes are necessary)
‐ XP205 Balance (MT-1106024)
TM
‐ Rondo 20 with PowerShower (MT-51108003)
Accessories
‐
‐
‐
‐
‐
‐
3 x Additional dosing unit (MT-51109030)
1 x 20 mL DV1020 glass burette (MT-51107502)
2 x 10 mL DV1010 glass burette (MT-51107501)
1 x 5 mL DV 1005 glass burette (MT-51107500)
100 mL Propylene titration beakers (MT-00101974)
®
LabX pro titration software
Results
All results
Method-ID
Sample
Dil.sample
NaOH
Formaldehyde
Sample
Dil.sample
NaOH
Formaldehyde
Sample
Dil.sample
NaOH
Formaldehyde
Sample
Dil.sample
NaOH
Formaldehyde
Sample
Dil.sample
NaOH
Formaldehyde
Sample
Dil.sample
NaOH
Formaldehyde
FCA
5 mL (1/6)
12.3 pH
16.30 g/L
13.25 g/L
5 mL (2/6)
12.3 pH
16.28 g/L
13.24 g/L
5 mL (3/6)
12.3 pH
16.30 g/L
13.15 g/L
5 mL (4/6)
12.3 pH
16.28 g/L
13.01 g/L
5 mL (5/6)
12.3 pH
16.26 g/L
12.91 g/L
5 mL (6/6)
12.3 pH
16.23 g/L
13.02 g/L
Method-ID
R1
Samples
Mean
s
srel
R2
Samples
Mean
s
srel
R4
Samples
Mean
s
srel
Cu
Dil.Sample
6
12.3
0.0
0 %
NaOH
6
16.28 g/L
0.03
0.164 %
Formaldehyde
6
13.10 g/L
0.14
1.053 %
Statistics
Titration curve: NaOH content
METTLER TOLEDO
Page 2 of 6
Titration Application M064
Table of measured values : NaOH content
Volume
mL
0.000
1.000
1.001
1.004
1.010
1.017
1.030
1.049
1.075
1.107
----------12.768
12.935
13.103
13.255
13.422
13.590
13.758
----------19.885
19.938
19.938
19.938
19.938
19.938
19.938
19.938
19.938
19.938
19.938
19.938
Increment
mL
NaN
1.000
0.001
0.003
0.006
0.007
0.013
0.019
0.026
0.032
------------------0.168
0.167
0.168
0.152
0.167
0.168
0.168
-------------------0.168
0.053
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Signal
pH
12.332
12.325
12.317
12.309
12.306
12.308
12.306
12.303
12.304
12.304
----------11.824
11.820
11.806
11.799
11.787
11.777
11.762
----------10.617
10.484
10.476
10.468
10.457
10.454
10.451
10.448
10.447
10.448
10.445
10.445
Change
pH
NaN
-0.007
-0.008
-0.008
-0.003
0.002
-0.002
-0.003
0.001
0.000
-------------0.016
-0.004
-0.014
-0.007
-0.012
-0.010
-0.015
-----------0.097
-0.133
-0.008
-0.008
-0.011
-0.003
-0.003
-0.003
-0.001
0.001
-0.003
0.000
Time
s
0
1
2
3
4
5
6
7
8
9
---------84
85
86
87
88
89
90
-------127
128
129
130
131
132
133
134
135
136
137
138
Temperature
°C
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
---------------------25.0
25.0
25.0
25.0
25.0
25.0
25.0
--------------------25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
Titration Curve: Formaldehyde content
METTLER TOLEDO
Page 3 of 6
Titration Application M064
Table of measured values : Formaldehyde content
Volume
mL
0.000
0.001
0.004
0.009
0.017
0.030
0.049
0.074
0.107
0.143
-------------------2.985
3.153
3.321
3.472
--------------------5.817
5.817
5.817
5.817
5.817
5.817
5.817
5.817
5.817
5.817
5.817
Increment
mL
NaN
0.001
0.003
0.005
0.008
0.013
0.019
0.025
0.33
0.036
--------------------------0.168
0.168
0.168
0.151
----------------------------0.002
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Signal
pH
11.615
11.615
11.614
11.618
11.612
11.617
11.611
11.608
11.607
11.608
---------------11.322
11.304
11.283
11.260
------------------10.497
10.494
10.494
10.494
10.487
10.492
10.492
10.486
10.489
10.489
10.483
Change
pH
NaN
0.000
-0.001
0.004
-0.006
0.005
-0.006
-0.003
-0.001
0.001
----------------------0.024
-0.018
-0.021
-0.023
--------------------0.006
-0.003
0.000
0.000
-0.007
0.005
0.000
-0.006
0.003
0.003
-0.006
Time
s
0
1
2
3
4
5
6
7
8
9
-----------30
31
32
33
-----------52
53
54
55
56
57
58
59
60
61
62
Temperature
°C
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
---------------------25.0
25.0
25.0
25.0
-----------------------25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
Comments
‐
‐
The electrode DGi111-SC is calibrated in the range of pH 9 to 12 (see application M004)
Titer determination of 0.1 mol/L HCl is done as application M003 and mean value found is 1.00031.
‐
The titrator displays warnings if upper or lower result limits are exceeded.
1. EP Titration :
Continuous endpoint titration to pH 10.5, i.e. the pH value of endpoint as indicated in the literature of the
manufacturer. This titration allows the determination of the NaOH content.
2. Calculation R2: NaOH content in g/L.
3. Calculation R3: Calculation of correction for NaOH in g/L. This value is the difference between the nominal value
of NaOH and the actual result. The nominal value is indicated by the manufacturer.
4. Dispense:
10mL sodium sulfite c(Na2SO3) = 1.0mol/L is dispensed. The pH value of this reagent must first be adjusted
according to the pH endpoint of the subsequent EP titration in this case pH 10.5
5. Stir: During stirring time the following reaction takes place:
HCHO + Na2SO3 + H2O → CH2OH•SO3Na + NaOH
Formaldehyde (HCHO) reacts with sodium sulfite, and sodium hydroxide is formed beside CH2OH•SO3Na.
6. EP Titration :
Continuous endpoint titration to pH 10.5, as indicated in the literature of the manufacturer. With this titration the
NaOH formed is titrated, and from the equivalent amount of NaOH the concentration of formaldehyde is
determined.
7. Calculation R4: Calculation of the formaldehyde content in g/L.
8. Calculation R5: Calculation of correction for formaldehyde in g/L. This value is the difference between the nominal
value of formaldehyde and the actual result. The nominal value is indicated by the manufacturer.
Bath Composition:
‐
‐
‐
This electroless alkaline copper bath is used for the deposition of relatively thick layers of copper on printed circuit
boards. The procedure is based on the chemical reduction of (weakly) complexed copper (II) ions at activated
catalytic surfaces.
This type of bath usually contains copper, complexing agent or mixture of complexing agents, alkali (e.g. NaOH),
formaldehyde as a reducing agent and additives.
The periodic bath control by titration is necessary for optimal application of the bath. The content of
copper (II) ions (see M062), of free complexing agents (see M063), of hydroxide and formaldehyde as
well as the pH value (this application) are determined. Concentrations values outside the limits cause
failure.
METTLER TOLEDO
Page 4 of 6
Titration Application M064
Method
001 Title
Type
Compatible with
ID
Title
. . .
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
Entry
Wait time
Control
Mode
Tendency
Endpoint value
Cotrol band
Dosing rate (max)
Dosing rate (min)
Termination
At EP
Termination delay
At Vmax
Max. time
Accompanying stating
Accompanying stating
Condition
Condition
General titration
T90
Cu
NaOH and Formaldehyde
1
Copper bath
Fixed volume
5.0 mL
1.0220 g/mL
1.0
25.0°C
Arbitrary
003 Titration stand (Rondo/TowerA)
Type
Rondo/TowerA
Titration stand
Rondo60/1A
Lid handling
No
004 Dispense (normal) [1]
Titrant
Concentration
Volume
Dosing rate
Condition
Cu Sample
1
5.0 mL
60.0 mL/min
No
005 Dispense (normal) [2]
Titrant
Concentration
Volume
Dosing rate
Condition
Water..
100
50.0 mL
60.0 mL/min
No
010 Calculation R2
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
011 Calculation R3
Result
Result unit
Formula
006 Stir
Speed
Duration
Condition
30%
10 s
No
007 Measure (normal) [1]
Sensor
Type
pH
Sensor
DGi111-SC
Unit
pH
Temperature acquisition
Temperature measurement
No
Stir
Speed
30%
Acquisition of measured values
Acquisition
Fix
Time
30
Mean value
No
Condition
Condition
No
008 Calculation R1
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
009 Titration (EP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Volume
METTLER TOLEDO
Dil.sample
pH
R1= E
C= 1
M[None]
z[None]
1
No
Yes
No
No
No
HCl
0.1 mol/L
pH
DGi111-SC
pH
No
30%
Volume
1.0 mL
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
012 Dispense (normal) [3]
Titrant
Concentration
Volume
Dosing rate
Condition
0 s
Absolute
Negative
10.5 pH
0.3 pH
10 mL/min
10 µL/min
Yes
10 s
30.0 mL
∞
No
No
NaOH
g/L
R2= Q1*C/m*d
C=M/z
M[Sodium hydroxide]
z[Sodium hydroxide]
2
No
Yes
No
No
No
Correction
g/L
R3=H[Nominal value_NaOH](Q1*C/m*d)
C=M/z
M[Sodium hydroxide]
z[Sodium hydroxide]
2
No
Yes
No
No
No
SODIUM SULFITE
1
10.0 mL
60.0 mL/min
No
013 Stir
Speed
Duration
Condition
Formula
014 Titration (EP) [2]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Wait time
Control
Mode
Tendency
Endpoint value
Cotrol band
Dosing rate (max)
Dosing rate (min)
Termination
At EP
Termination delay
At Vmax
Max. time
Page 5 of 6
30%
60 s
Yes
R2>0
HCL
0.1 mol/L
pH
DGi111-SC
pH
No
30%
None
0
Absolute
Negative
10.5 pH
0.2 pH
10 mL/min
10 µL/min
Yes
10 s
30.0 mL
∞
Titration Application M064
Accompanying stating
Accompanying stating
Condition
Condition
Formula
015 Calculation R4
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
Formula
016 Calculation R5
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
Formula
017 Instruction
Instruction
Mode
Print
LabX command
Condition
Formula
018 Instruction
Instruction
Mode
Print
LabX command
Condition
Formula
019 Instruction
Instruction
Mode
Print
LabX command
Condition
Formula
020 Instruction
Instruction
Mode
Print
LabX command
Condition
Formula
021 Rinse
Auxillary reagent
Rinse cycles
Vol.per cycle
Position
Drain
Condition
METTLER TOLEDO
022 Condition
Type
Interval
Position
Time
Speed
Condition
No
Yes
R2>0
Formaldehyde
g/L
R4=Q[2]*C*H[Factor for 37%
formaldehyde]/m*d
C=M/z
M[Formaldehyde]
z[Formaldehyde]
2
No
Yes
No
No
Yes
R2>0
Fix
1
Conditioning beaker
10 s
30 %
No
023 End of sample
Correction
g/L
R5=H[Nominal value
Formaldehyde](Q[2]*C*H[Factor for 37%
formaldehyde]/m*d
C=M/z
M[Formaldehyde]
z[Formaldehyde]
2
No
Yes
No
No
Yes
R2>0
Sodium hydroxide content too
high…PLEASE CORRECT
Confirmation
Yes
No
Yes
R2>H[Upper limit for NaOH]
Sodium hydroxide content too
low…PLEASE CORRECT
Confirmation
Yes
No
Yes
R2<H[Lower limit for NaOH]
Formaldehyde content too
high…PLEASE CORRECT
Confirmation
Yes
No
Yes
R4>H[Upper limit for
Formaldehyde]
Formaldehyde content too
low…PLEASE CORRECT
Confirmation
Yes
No
Yes
R4<H[Upper limit for
Formaldehyde]
WATER
1
10 mL
Current position
No
No
Page 6 of 6
Titration Application M064
METTLER TOLEDO
Application M065
Electroless Nickel Bath: Determination of Sodium Hypophosphite
Method for determination of sodium hypophosphite content in electroless nickel bath by iodometric back
titration.
Sample
Preparation and Procedures
Electroless nickel bath, 3 mL
CAUTION
Compound
Chemicals
Titrant
Sodium hypophosphite (NaH2PO2)
M = 87.97 g/mol, z = 2
Sodium hypophosphite monohydrate
(NaH2PO2.H2O)
M = 105.99 g/mol, z = 2
20% Sulfuric acid 50mL, 1 g
Potassium iodide, 0.1M HCl
50 mL, 0.1 mol/L ½ I2 20 mL.
Potassium iodate, KIO3
20-30 mg
Indication
DMi140-SC
Combined platinum ring
electrode
Chemistry
I2 + H2PO2 + H2O  2I +
2+
HPO3 + 3H
-
Waste
disposal
Author,
Version
METTLER TOLEDO
-
Ensure accurate cleaning of sensor is sufficient after
each titration.
Sample handling (Electroless nickel bath)
Add 6mL of Ginplate Ni 418-A and 9 mL of Ginplate Ni
418-B in 100mL volumetric flask and make up the
volume with deionized water. Shake it properly and then
use it as sample.
-
Take 3 mL of Nickel bath sample in 100 mL titration
beaker with graduated pipette. Add 50 mL sulfuric
acid with 50 mL glass cylinder.
-
Add 20 mL ½ I2 with the help of external dosing unit.
After the addition of iodine immediately cover the
sample beaker tightly with a lid. Keep the beaker in
dark (60 min) for oxidation reaction.
-
Place the oxidized sample beaker on sample changer
-
Titrate with 0.1mol/L Na2S2O3.
After completion of each sample, electrode, stirrer
and titration tubes will be rinsed by deionized water by
means of membrane pump.
Electrode is cleaned first with water in condition
beaker placed on sample changer after each sample.
Back value (Method 065b)
-
2Na2S2O3 + I2 → Na2S4O6 +
2NaI
Calculation
Use safety goggles, a lab coat and wear gloves. If
possible, work in a fume hood.
Sample titration (Method 065a)
Sodium thiosulfate, Na2S2O3
c( Na2S2O3)=0.1 mol/L
Standard
-
-
Perform back value similar to sample determination
except the addition of sample and same precautious
has to be taken as that of sample.
-
The back value is determined and stored as B[Back
Value]
Remarks
R1 = (B – Q) *C/m*d, g/L
R2 = (B – Q) *C/m*d, g/L
R3 = [H-(B – Q)]*C/m*d, g/L
B = Back value
H = Nominal value
C = M/z
Q = Titrant consumption in mmol.
m = mass of the sample in mL
d = Density of the sample
M =Molar mass of sample in g.
z = Equivalent number of sample
Nickel solutions: If necessary,
neutralize the solution before
final disposal as special waste.
Geeta Naik, IMSG AnaChem, V2.0
Revised: C. De Caro, MSG AnaChem
‐
Prior to use, adjust the automated titration stand by
turning the small knob on the housing at 7 for rinsing
and conditioning.
‐
The setting of the automated titration stand allows
rinsing of 2 secs and a conditioning of 30 secs the
electrode is crucial to achieve accurate and precise
results.
‐
The application method has been developed for the
mentioned sample. It may be necessary to optimize
the method for your sample.
‐
Purity of potassium iodate used is 99.5%.
‐
Literature:
Mettler-Toledo Application M065 and M009
GINPLATE Ni 418 (http://www.growel.com/tds/563.pdf)
Page 1 of 5
Titration Application M065
Instruments
‐ Titration Excellence T90
(Other Titrators: depending on instrument type, manual operation and method
changes are necessary)
‐ XP205 Balance
Accessories
‐
‐
‐
‐
‐
Rondolino Sample Changer (MT-51108500)
PP Titration beakers 100 mL (MT-00101974)
Spatula
®
Lab X pro titration software
1 x 20 mL DV1020 glass burette (MT-51107502)
Results
All results
Method-ID
Sample
R1 (NaH2PO2.H2O)
R2 (NaH2PO2.H2O)
R3 (Correction)
Sample
R1 (NaH2PO2.H2O)
R2 (NaH2PO2.H2O)
R3 (Correction)
Sample
R1 (NaH2PO2.H2O)
R2 (NaH2PO2.H2O)
R3 (Correction)
Sample
R1 (NaH2PO2.H2O)
R2 (NaH2PO2.H2O)
R3 (Correction)
Sample
R1 (NaH2PO2.H2O)
R2 (NaH2PO2.H2O)
R3 (Correction)
Sample
R1 (NaH2PO2.H2O)
R2 (NaH2PO2.H2O)
R3 (Correction)
Sodiumhypophosphite
3 mL (1/6)
23.17 g/L
27.92 g/L
1.08 g/L
3 mL (2/6)
23.21 g/L
27.96 g/L
1.04 g/L
3 mL (3/6)
23.17 g/L
27.91 g/L
1.09 g/L
3 mL (4/6)
23.11 g/L
27.85 g/L
1.15 g/L
3 mL (5/6)
23.14 g/L
27.87 g/L
1.13 g/L
3 mL (6/6)
23.15 g/L
27.89 g/L
1.11 g/L
Method-ID
R2
Samples
Mean
s
srel
Sodiumhypophosphite
NaH2PO2.H2O
6
27.90
0.04
0.140 %
Statistics
Titration curve
METTLER TOLEDO
Page 2 of 5
Titration Application M065
Table of measured values
EQP1
Volume
mL
0.000
0.050
0.100
0.200
0.300
0.400
0.500
0.600
0.700
0.800
---------3.800
3.900
4.000
4.100
4.200
4.300
4.400
4.500
4.560
4.586550
4.610
4.660
4.755
4.847
4.947
5.047
5.147
5.247
5.347
5.1000
Increment
mL
NaN
0.050
0.050
0.100
0.100
0.100
0.100
0.100
0.100
0.100
------------------0.100
0.100
0.100
0.100
0.100
0.100
0.100
0.100
0.060
NaN
0.050
0.050
0.095
0.092
0.100
0.100
0.100
0.100
0.100
0.100
Signal
mV
286.1
286.4
285.9
286.4
285.7
285.6
286.0
284.9
285.6
284.7
----------267.8
267.0
264.4
262.8
259.8
254.9
248.8
238.4
219.5
199.9
182.5
170.0
156.0
151.2
146.6
142.9
138.7
136.9
134.1
132.7
Change
mV
NaN
0.3
-0.5
0.5
-0.7
-0.1
0.4
-1.1
0.7
-0.9
-------------1.8
-0.8
-2.6
-1.6
-3.0
-4.9
-6.1
-10.4
-18.9
NaN
-37.0
-12.5
-14.0
-4.8
-4.6
-3.7
-4.2
-1.8
-2.8
-1.4
1st deriv.
mV/mL
NaN
NaN
NaN
NaN
NaN
-2.05
-1.50
-2.11
-1.86
-2.00
---------------14.68
-15.98
-18.34
-19.32
-19.78
-59.23
-145.04
-223.79
-268.61
-272.34
-271.88
-228.13
-153.43
-69.92
-30.65
NaN
NaN
NaN
NaN
NaN
Time
s
0
2
4
7
9
12
14
16
18
21
--------93
96
99
102
106
108
111
113
120
NaN
132
140
150
154
158
161
166
168
172
175
Temperature
°C
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
----------------------25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
NaN
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
Comments
‐
This electroless nickel bath is used for chemical nickel deposition on printed circuit boards. It consists
of nickel salts, sodium hypophosphite, buffering compounds, stabilizers, accelerators, wetting and
complexing agents. Decomposition products are formed during use of the bath.
‐
Titer determination of 0.1 mol/L Na2S2O3 is done as application M009 and mean value found is
0.99507. The mean value of the titer is automatically stored as part of the setup by the function TITER.
‐
Standardization of Na2S2O3: Weigh about 25 mg of potassium iodate, dissolve it in 50 mL 0.1M HCl,
add 1 g KI immediate before titration and titrate with 0.1 mol/L Na2S2O3.
‐
The mean back value of a series of three samples is automatically stored as auxillary value or back
value B and can therefore by applied by method 065a for determination of nickel.
‐
The storage of the mean value only occurs if it is comprised between the limits 1.5 and 2.5 mmol which
assure an adequate concentration.
‐
The shelf life of the iodine solution is limited. We recommend performing back value method before
each nickel content determination.
‐
The titrator displays warnings if upper or lower result limits are exceeded. The upper or lower result
limits are saved as nominal values and is given in the auxillary value H[Nominal Value for NaH2PO3]
etc.
‐
Oxidation is carried out at room temperature in the dark. Cover the beaker to prevent loss of iodine,
the reaction requires 60 minutes to complete.
METTLER TOLEDO
Page 3 of 5
Titration Application M065
Method 065a (Sample titration) and Method 065b (Back value)
001 Title
Type
Compatible with
ID
Title
. . .
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
General titration
T90
Sodiumhypophosphite
Determination of NaH2PO3 low
008 Calculation R3
Result
Result unit
Formula
1
___
Fixed volume
3 mL
1.04 g/mL
1.0
25.0°C
Constant
M
Z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
003 Titration stand (Rondolino TTL)
Type
Rondolino TTL
Titration stand
Rondolino TTL 1
004 Stir
Speed
Duration
Condition
005 Titration (EQP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Wait time
Control
Control
Titrant addition
dE (set value)
dV (min)
dV (max)
Mode
dE
dt
t (min)
t (max)
Evaluation and recognition
Procedure
Threshold
Tendency
Ranges
Add. EQP criteria
Termination
At Vmax
At potential
At slope
After number of
recognized EQPs
Number of EQPs
Combined termination
criteria
40%
5 s
No
009 Instruction
Instruction
Mode
Print
LabX command
Condition
Formula
Na2S2O3
0.1 mol/L
mV
DM140-SC
mV
010 Instruction
Instruction
No
Mode
Print
LabX command
Condition
Formula
40%
None
0 s
User
Dynamic
8 mV
0.05 mL
0.1 mL
Equilibrium controlled
1.0 mV
2 s
2 s
12 s
Correction
g/L
R3=H[Nominal Value for
NaH2PO3]-((B[Back Value]Q)*C/m*d)
C=M/z
M[NaH2PO3.H2O]
z[NaH2PO3.H2O]
2
No
Yes
No
No
No
Sodium hypophosphite
monohydrate content too high
Confirmation
Yes
No
Yes
R2>H[Upper limit of NaH2PO3]
Sodium hypophosphite
monohydrate content too low
Confirmation
Yes
No
Yes
R2<[Lower limit of NaH2PO3]
011 End of sample
Standard
100
Negative
0
No
20 mL
No
No
Yes
1
No
006 Calculation R1
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
NaH2PO3
g/L
R1=(B[Back Value]-Q)*C/m*d
C=M/z
M[NaH2PO3]
z[NaH2PO3]
2
No
Yes
No
No
No
007 Calculation R2
Result
Result unit
Formula
Constant
M
NaH2PO3.H2O
g/L
R2=(B[Back Value]-Q)*C/m*d
C=M/z
M[NaH2PO3.H2O]
METTLER TOLEDO
z[NaH2PO3.H2O]
2
No
Yes
No
No
No
Page 4 of 5
Titration Application M065
001 Title
Type
Compatible with
ID
Title
. . .
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
General titration
T50/T70/T90
BackValue
Back Value
1
---Fixed volume
20.0 mL
1.0 g/mL
1.0
25 °C
003 Titration stand (Rondolino TTL)
Type
Rondolino TTL
Titration stand
Rondolino TTL 1
008 Blank
Name
Value B =
Unit
Limits
Condition
Back Value
Mean[R1]
mmol
No
No
009 Calculation R2
Result
Result unit
Formula
Constant C =
M
z
Decimal places
Result limits
Record statistics
Send to buffer
Condition
Mean Back Value
mmol
R2=Mean[R1]
1
M[None]
z[None]
3
No
Yes
No
No
004 Stir
Speed
Duration
Condition
005 Titration (EQP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Volume
Wait time
Control
Control
Titrant addition
dE (set value)
dV (min)
dV (max)
Mode
dE
dt
t (min)
t (max)
Evaluation and recognition
Procedure
Threshold
Tendency
Ranges
Add. EQP criteria
Termination
At Vmax
At potential
At slope
After number of
recognized EQPs
Number of EQPs
Combined termination
criteria
Accompanying stating
Accompanying stating
Condition
Condition
006 Calculation R1
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
30 %
10 s
No
Na2S2O3
0.1 mol/L
mV
DM140-SC
mV
No
40%
Volume
15 mL
0 s
User
Dynamic
4 mV
0.1 mL
0.5 mL
Equilibrium controlled
1.0 mV
3 s
3 s
30 s
Standard
150
None
0
No
30 mL
No
No
Yes
1
Yes
No
No
Consumption
mmol
R1=Q
C=1
M[None]
z[None]
4
No
Yes
No
No
No
007 End of sample
METTLER TOLEDO
Page 5 of 5
Titration Application M065
METTLER TOLEDO
Application M066
Electroless Nickel Bath: Determination of Nickel
Method for determination of nickel content in electroless nickel bath.
Sample
Compound
Chemicals
Electroless nickel bath, 5 mL
Preparation and Procedures
Nickel, Ni
M= 58.69 g/mol, z = 1
CAUTION
‐ Use safety goggles, a lab coat and wear gloves.
If possible, work in a fume hood.
‐ Ensure accurate cleaning of sensor is sufficient
after each titration.
Deionized water, 50 mL
Indicator : 0.2 g Murexide
trituration with NaCl (1 : 500).
Buffer pH10, 10 mL
Titrant
Ethylenediaminetetraacetic acid
disodium, C10H14N2Na2O8•2H2O
c(EDTA- Na2) = 0.1 mol/L
Standard
Zinc Sulfate, ZnSO4
c( ZnSO4) = 0.1 mol/L
Indication
DP5 Phototrode (555 nm)
(Yellow to blue-violet)
Chemistry
Ni + Murexide →
+
Ni-Murexide
TM
2+
+
Remarks
‐
4-
R = Q*C/m*d, g/L
Q = Titrant consumption in mmol.
C = M/z.
M = Molar mass of sample in g.
z = Equivalent no. sample, z=1
d = density of sample in g/mL.
m = mass of sample in mL.
Waste
disposal
Sample titration:
‐ Add 0.25 g murexide trituration with NaCl
(1:500) in the beaker placed on sample changer.
‐ Dispense 5 mL sample from dosing unit.
‐ Add 50 mL of deionized water from dosing unit.
‐ Add 10 mL of buffer pH10 from dosing unit.
‐ Titrate with 0.1mol/L EDTA.
‐ After completion of each sample sensor, stirrer
and titration tubes are rinsed by deionized water
by means of membrane pump.
‐ Sensor is cleaned with deion. water in the
conditioning beaker placed on sample changer
after each sample.
-
Ni-Murexide + EDTA →
2Ni-EDTA + Murexide
Calculation
Sample Preparation:
‐ Electroless nickel bath : Pipette 20 mL
Ginplate Ni 426-A and 20 mL Ginplate Ni 426-B
in 200 mL volumetric flask and dilute it upto the
mark with deionized water.
Nickel solutions : If necessary,
neutralize the solution before
final disposal as special waste.
Prior to use , adjust the output signal of the DP5
TM
Phototrode to approx. 1000 mV in deion.water
before starting titration (100% transmission) by
turning the small knob on the housing.
‐ Rinsing and conditioning of the Phototrode is
crucial to achieve accurate and precise results.
‐ Avoid formation of bubbles during titration by low
speed rate of stirrer, as they disturb photometric
indication.
‐ This method allows a fully automated analysis
procedure. This method can be easily modified
for manual operation. Select “Manual stand” in
the method function “Titration stand”.
‐ Sample may be added manually using a pipette
instead of using an additional dosing unit.
Literature :
‐
Author,
Version
METTLER TOLEDO
Ruby Das, IMSG AnaChem, V2.0
Revised: C. De Caro, MSGAnaChem
‐
Page 1 of 4
Ginplate NI 426, ( http://www.growel.com/tds/549.pdf), a
trademark of Grauer & Weil India Ltd, www.growel.com
Mettler-Toledo Application M066 and M007
Titration Application M066
Instruments
‐ Titration Excellence T50/T70/T90
(Other Titrators: depending on instrument type, manual operation and method
changes are necessary)
‐ XP205 Balance (MT-1106024)
TM
‐ Rondo 20 with PowerShower (MT-51108003)
Accessories
‐
‐
‐
‐
‐
3 x Additional dosing unit (MT-51109030)
1 x 20 mL DV1020 glass burette (MT-51107502)
2 x 10 mL DV1010 glass burette (MT-51107501)
1 x 5 mL DV 1005 glass burette (MT-51107500)
100 mL Propylene titration beakers (MT-00101974)
®
Results
All results
Method-ID
Sample
R1 (Nickel)
Sample
R2 (Nickel)
Sample
R3 (Nickel)
Sample
R4 (Nickel)
Sample
R5 (Nickel)
Sample
R6 (Nickel)
Nickel determination
5 mL (1/6)
5.44 g/L
5 mL (2/6)
5.44 g/L
5 mL (3/6)
5.45 g/L
5 mL (4/6)
5.43 g/L
5 mL (5/6)
5.43 g/L
5 mL (6/6)
5.44 g/L
Method-ID
R1
Samples
Mean
s
srel
Nickel determination
Nickel
6
5.44
0.01
0.138%
Statistics
Titration curve
METTLER TOLEDO
Page 2 of 4
Titration Application M066
Table of measured values
EQP1
Volume
mL
0.000
0.5715
0.8570
1.0000
1.1000
1.2000
1.3000
1.4000
1.5000
1.6000
1.7000
1.8000
1.9000
2.0000
2.1000
-----------4.3440
4.3940
4.4440
4.4940
4.540268
4.5440
4.5940
4.6440
4.6940
4.7600
4.8600
4.9600
5.0600
5.1600
5.2600
Increment
mL
NaN
0.5715
0.2855
0.1430
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
0.1000
------------------0.0500
0.0500
0.0500
0.0500
NaN
0.0500
0.0500
0.0500
0.0500
0.6600
0.1000
0.1000
0.1000
0.1000
0.1000
Signal
mV
757.2
748.2
739.0
738.4
734.0
732.1
729.6
727.1
723.3
721.7
720.6
716.7
713.5
713.0
708.5
--------518.0
499.4
476.6
446.3
420.7
418.6
379.1
339.4
322.0
320.1
319.3
319.6
320.4
321.2
321.9
Change
mV
NaN
-9.0
-9.2
-0.6
-4.4
-1.9
-2.5
-2.5
-3.8
-1.6
-1.1
-3.9
-3.2
-0.5
-4.5
-----------17.4
-18.6
-22.8
-30.3
NaN
-27.7
-39.5
-39.7
-17.4
-1.9
-0.8
0.3
0.8
0.8
0.7
1st deriv.
mV/mL
NaN
NaN
NaN
NaN
NaN
-25.96
-24.64
-26.16
-24.72
-24.40
-23.28
-24.36
-28.28
-29.78
-30.43
---------------358.17
-421.44
-538.07
-658.13
-659.56
-657.52
-544.67
-393.50
-269.40
-148.20
NaN
NaN
NaN
NaN
NaN
Time
s
0
5
13
16
20
24
28
32
37
42
44
50
55
58
62
-----184
190
196
202
NaN
210
218
230
239
243
245
248
250
253
255
Temperature
°C
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
----------25.0
25.0
25.0
25.0
NaN
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
Comments
‐
‐
‐
‐
‐
‐
Titer determination of 0.1 mol/L EDTA-Na2 is done as per the Mettler –Toledo method application
M007 and mean value found is 0.99163.
The mean value of the titer is automatically stored as part of the setup by the function TITER.
The buffer pH 10 is prepared by dissolving 64 g NH4Cl in 600mL 25% Ammonia solution and diluting it
upto the mark with deionized water in a 1L volumetric flask..
The shape of the titration curve is somewhat affected by the concentration of the indicator. The results,
however do not differ significantly ( tested range: 25-500 mg of Murexide trituration with NaCl(1 :500).
Add the indicator before starting analysis. Keep sample free of air bubbles during titration. Air bubbles
and undissolved impurities affect the photometric indication.
Due to the steep signal change, an EQP titration with fixed increments is used. The low threshold
value allows for different amounts of indicator.
Principle :
‐ Nickel ions forms yellow complex with murexide in alkaline solution:
2+
+
Ni
+ Murexide → Ni-Murexide
‐
By adding EDTA , Ni forms a more stable complex with EDTA:
Ni-Murexide + EDTA
→ Ni-EDTA
+ Murexide
At the equivalence point, all Ni ions have been complexed by EDTA and murexide is free in the alkaline
solution. There is a colour change from yellow to blue-violet.
+
METTLER TOLEDO
4-
2-
Page 3 of 4
-
Titration Application M066
Method
001 Title
Type
Compatible with
ID
Title
. . .
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
Entry
Number of EQPs
Combined termination
criteria
Accompanying stating
Accompanying stating
Condition
Condition
General titration
T50 / T70 / T90
Nickeldetermination
Ni determination
1
Nickel
Fixed volume
5.0 mL
1.03 g/mL
1.0
25.0°C
Arbitrary
003 Titration stand (Rondo/TowerA)
Type
Rondo/TowerA
Titration stand
Rondo60/1A
Lid handling
No
004 Dispense (normal) [1]
Titrant
Concentration
Volume
Dosing rate
Condition
NI SAMPLE
1
5.0 mL
60.0 mL/min
No
005 Dispense (normal) [2]
Titrant
Concentration
Volume
Dosing rate
Condition
Water..
1
50.0 mL
60.0 mL/min
No
006 Dispense (normal) [3]
Titrant
Concentration
Volume
Dosing rate
Condition
BUFFER 10PH
1
10.0 mL
60.0 mL/min
No
1
No
No
No
009 Calculation R1
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
Ni content
g/L
R1= Q*C/m*d
C=M/z
M[Nickel]
z[Nickel]
2
No
Yes
No
No
No
010 Rinse
Auxillary reagent
Rinse cycles
Vol.per cycle
Position
Drain
Condition
WATER
1
10 mL
Current position
No
No
011 Condition
Type
Interval
Position
Time
Speed
Condition
Fix
1
Conditioning beaker
20 s
10 %
No
012 End of sample
007 Stir
Speed
Duration
Condition
008 Titration (EQP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Volume
Wait time
Control
Control
Titrant addition
dE (set value)
dV (min)
dV (max)
Mode
dE
dt
t (min)
t (max)
Evaluation and recognition
Procedure
Threshold
Tendency
Ranges
Add. EQP criteria
Termination
At Vmax
At potential
At slope
After number of
recognized EQPs
METTLER TOLEDO
10%
60 s
No
EDTA(0.1M)
0.1 mol/L
Phototrode
DP5
mV
No
10%
Volume
1.0
0 s
User
Dynamic
10 mV
0.05 mL
0.1 mL
Equilibrium controlled
1.0 mV
2 s
2 s
12 s
Standard
200.0 mV/mL
None
0
No
10.0 mL
No
No
Yes
Page 4 of 4
Titration Application M066
METTLER TOLEDO
Application M067
Electroless Nickel Bath: Determination of Sodium Orthophosphite
Method for determination of Sodium orthophosphite content in electroless nickel bath by iodometric back
titration.
Sample
Electroless nickel bath, 0.5 mL
Preparation and Procedures
CAUTION
Compound
Chemicals
‐
Disodium hydrogen phosphite
(Na2HPO3)
M = 125.96 g/mol, z = 2
Sodium dihydrogenphosphite
(NaH2PO2)
M = 105.99 g/mol, z = 2
Phosphorous acid (H3PO3)
M = 81.99 g/mol, z = 2
Use safety goggles, a lab coat and wear gloves. If
possible, work in a fume hood.
Ensure accurate cleaning of sensor is sufficient after
each titration.
‐
Sample handling
Electroless Nickel bath: Take 6 mL of Ginplate Ni 418-A
and 9 mL of Ginplate Ni 418-B in 100 mL volumetric flask
and make up the volume with deionized water. Shake it
properly and then use it as sample.
20mL 2 M Acetic acid (CH3COOH),
1 g Potassium iodide (KI),
Sample titration
20 mL 5% Sodium hydrogen carbonate
(NaHCO3)
‐
20 mL 0.1 M ½ I2 Iodine ,
‐
Take 0.5 mL of electroless nickel bath sample in 100
mL titration beaker with a 1 mL pipette.
Add 5 % sodium bicarbonate 20 mL in 100 mL
titration beaker with a 25 mL glass cylinder
Add 20 mL ½ I2 with help of external dosing unit. After
the addition of iodine immediately cover the beaker to
avoid loss of released iodine.
Keep it in dark for 30 min for oxidation reaction
Place the oxidized sample on sample.
Immediately before titration the sample is acidified by
adding 2 mol/L acetic acid 20 mL with additional
dosing unit.
Titrate with 0.1mol/L Na2S2O3
After completion of each sample, electrode, stirrer
and titration tubes will be rinsed by deionized water by
means of membrane pump
Electrode is cleaned first with water in condition
beaker placed on sample changer after each sample.
50 mL 0.1 M HCl
‐
Titrant
Sodium thiosulfate, Na2S2O3
c(Na2S2O3) = 0.1 mol/L
Standard
Potassium iodate, KIO3
20-30 mg
Indication
DMi140-SC
Combined platinum ring
electrode
Chemistry
I2 + HPO3
32I + PO4
+
+
2Na2S2O3
Na2S4O6
I2
→
2NaI
Calculation
2-
+
+
‐
‐
‐
‐
‐
-
3OH
2H2O
→
Blank (or Back) value
‐
‐
R1 = (B – Q) *C/m*d, g/L
R2 = (B – Q) *C/m*d, g/L
R3 = (B – Q) *C/m*d, g/L
Author,
Version
METTLER TOLEDO
Perform blank similar to sample determination
except the addition of sample and same precautious
has to be taken as that of sample..
The back value is determined and stored as B[Back
Value ophosphite]
Remarks
B = Back value
C = M/z
Q = Titrant consumption in mmol.
m = mass of the sample in mL
d = Density in g/mL
M =Molar mass of sample in g.
z = Equivalent number of sample
Waste
disposal
‐
‐
‐
Nickel solutions: If necessary,
neutralize the solution before
final disposal as special waste.
Geeta Naik, IMSG AnaChem, V 2.0
Revised: C. De Caro, MSG AnaChem
‐
‐
‐
Page 1 of 5
Prior to use, adjust automated titration stand by
turning the small knob on the housing of the stand at
pos. 7 for electrode conditioning.
The setting allows for rinsing (2 s) and conditioning
(30 s) of the electrode. This is crucial for accurate and
precise results.
The application method has been developed for the
mentioned sample. It may be necessary to optimize
the method for your sample.
Purity of potassium iodate used is 99.5%.
Literature:
Mettler-Toledo Application M067 and M009.
GINPLATE Ni 418 (www.growel.com/tds/563.pdf )
Titration Application M067
Instruments
‐ Titration Excellence T90
(Other Titrators: depending on instrument type, manual operation and method
changes are necessary)
‐ XP205 Balance
Accessories
‐
‐
‐
‐
‐
‐
1 x 20 mL DV1020 glass burette (MT-51107502)
1 x Additional dosing unit (MT-51109030
PP Titration beakers 100 mL (MT-00101974)
Rondolino Automate Titration Stand (MT-51108500)
®
LabX pro titration software
Spatula
Results
All results
Method-ID
Sample
R1 (Na2HPO3)
R2 (NaH2PO3)
R3 (H3PO3)
Sample
R1 (Na2HPO3)
R2 (NaH2PO3)
R3 (H3PO3)
Sample
R1 (Na2HPO3)
R2 (NaH2PO3)
R3 (H3PO3)
Sample
R1 (Na2HPO3)
R2 (NaH2PO3)
R3 (H3PO3)
Sample
R1 (Na2HPO3)
R2 (NaH2PO3)
R3 (H3PO3)
Sample
R1 (Na2HPO3)
R2 (NaH2PO3)
R3 (H3PO3)
Orthophosphite
0.5 mL (1/6)
9.90 g/L
8.18 g/L
6.45 g/L
0.5 mL (2/6)
9.97 g/L
8.23 g/L
6.49 g/L
0.5 mL (3/6)
9.92 g/L
8.19 g/L
6.46 g/L
0.5 mL (4/6)
10.17 g/L
8.40 g/L
6.62 g/L
0.5 mL (5/6)
10.25 g/L
8.46 g/L
6.67 g/L
0.5 mL (6/6)
10.38 g/L
8.57 g/L
6.76 g/L
Method-ID
R1
Samples
Mean
s
srel
orthophosphite
Na2HPO3
6
10.10
0.20
1.956 %
Statistics
Titration curve
METTLER TOLEDO
Page 2 of 5
Titration Application M067
Table of measured values
EQP1
Volume
mL
0.000
8.571
12.857
15.000
15.100
15.200
15.300
15.400
15.500
15.600
---------18.900
19.000
19.100
19.200
19.300
19.400
19.461
19.511
19.561
19.598967
19.611
19.661
19.711
19.811
19.911
20.011
20.061
20.161
20.261
20.361
Increment
mL
NaN
8.571
4.286
2.143
0.100
0.100
0.100
0.100
0.100
0.100
------------------0.100
0.100
0.100
0.100
0.100
0.100
0.061
0.050
0.050
NaN
0.050
0.050
0.050
0.100
0.100
0.100
0.050
0.100
0.100
0.100
Signal
mV
407.5
398.9
391.0
385.1
385.5
385.0
384.5
384.0
384.1
383.7
----------358.7
357.1
354.1
351.3
347.6
342.5
338.3
333.4
324.6
302.8
295.9
261.4
257.0
254.1
251.6
238.3
236.5
235.2
234.0
232.7
Change
mV
NaN
-8.6
-7.9
-5.9
0.4
-0.5
-0.5
-0.5
0.1
-0.4
-------------1.6
-1.6
-3.0
-2.8
-3.7
-5.1
-4.2
-4.9
-8.8
NaN
-28.7
-34.5
-4.4
-2.9
-2.5
-13.3
-1.8
-1.3
-1.2
-1.3
1st deriv.
mV/mL
NaN
NaN
NaN
NaN
NaN
-3.01
-3.26
-3.14
-3.59
-3.16
---------------17.69
-21.10
-26.09
-32.66
-43.74
-99.50
-154.43
-235.82
-305.97
-307.25
-290.90
-251.16
-191.85
-100.31
-35.71
NaN
NaN
NaN
NaN
NaN
Time
s
0
12
20
25
59
62
66
69
72
76
--------189
193
197
200
204
207
211
214
218
NaN
222
237
241
244
248
278
281
284
288
292
Temperature
°C
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
----------------------25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
NaN
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
Comments
•
This electroless nickel bath is used for chemical nickel deposition on printed circuit boards. It consists
of nickel salts, sodium hypophosphite, buffering compounds, stabilizers, accelerators, wetting and
complexing agents. Decomposition products are formed during use of the bath.
•
Titer determination of 0.1mol/L Na2S2O3 is done as per the Mettler-Toledo method application M009
and mean value found is 0.99896. The mean value of the titer is automatically stored as part of the
setup by the function TITER.
•
Standardization of Na2S2O3: Weigh about 25 mg of potassium iodate, dissolve it in 50 mL mol/L HCl
add 1 g KI immediate before titration and titrate with 0.1 mol/L Na2S2O3
•
The mean value of a series of three samples is automatically stored as auxillary value or back value
B and can therefore applied by method content determination for determination of nickel.
•
The storage of the mean value only occurs if it is comprised between the limits 1.5 and 2.5 mmol
which assure an adequate concentration.
•
The shelf life of the iodine solution is limited. We recommend performing back value method before
each nickel content determination.
•
If the orthophosphite concentration exceeds the limit given as per the sample e.g. 20 g/L, an
instruction is displayed.
•
Oxidation is carried out at room temperature in the dark. Cover the beaker to prevent loss of iodine,
the reaction requires 30 minutes to complete.
METTLER TOLEDO
Page 3 of 5
Titration Application M067
Method
001 Title
Type
Compatible with
ID
Title
. . .
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
General titration
T90
orthophosphite
EQP
z
1
-Fixed volume
0.5 mL
1.03 g/mL
1.0
25.0°C
003 Titration stand (Rondolino TTL)
Type
Rondolino TTL
Titration stand
Rondolino TTL 1
004 Dispense (normal) [1]
Titrant
Concentration
Volume
Dosing rate
Condition
007 Calculation R1
Result
Result unit
Formula
Constant
M
Acetic acid
2 mol/L
20 mL
60.0 mL/min
No
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
008 Calculation R2
Result
Result unit
Formula
Constant
M
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
NaH2PO3
g/L
R2=(B[Back Value]-Q)*C/m*d
C=M/z
M[Sodium dihydrogen
phosphite]
z[Sodium dihydrogen
phosphite]
2
No
Yes
No
No
No
009 Calculation R3
Result
Result unit
Formula
Constant
M
Z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
H3PO3
g/L
R3=(B[Back Value]-Q)*C/m*d
C=M/z
M[Phosphoric acid]
z[Phosphoric acid]
2
No
Yes
No
No
No
z
005 Stir
Speed
Duration
Condition
006 Titration (EQP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Volume
Wait time
Control
Control
Titrant addition
dE (set value)
dV (min)
dV (max)
Mode
dE
dt
t (min)
t (max)
Evaluation and recognition
Procedure
Threshold
Tendency
Ranges
Add. EQP criteria
Termination
At Vmax
At potential
At slope
After number of
recognized EQPs
Number of EQPs
Combined termination
criteria
Accompanying stating
Accompanying stating
Condition
Condition
METTLER TOLEDO
30%
10 s
No
Na2S2O3
0.1 mol/L
mV
DM140-SC
mV
No
30%
Volume
15 mL
30 s
User
Dynamic
4.0 mV
0.05 mL
0.1 mL
Equilibrium controlled
1.0 mV
3 s
3 s
30 s
Na2HPO3
g/L
R1=(B[Back Value]-Q)*C/m*d
C=M/z
M[Di Sodium hydrogen
phosphite]
z[Di Sodium hydrogen
phosphite]
2
No
Yes
No
No
No
010 Instruction
Instruction
Mode
Print
LabX command
Condition
Formula
Check concentration of
phosphite
Confirmation
Yes
No
Yes
R2>H[Nominal value for
NaH2PO3(o)]
011 End of sample
Standard
200
None
0
No
30
No
No
Yes
1
No
No
No
Page 4 of 5
Titration Application M067
001 Title
Type
Compatible with
ID
Title
. . .
002 Sample
Number of IDs
ID 1
Entry type
Volume
Density
Correction factor
Temperature
General titration
T50/T70/T90
BackValueOphosphite
Back Value of Orthophosphite
1
-Fixed volume
20 mL
1.0 g/mL
1.0
25.0°C
003 Titration stand (Rondolino TTL)
Type
Rondolino TTL
Titration stand
Rondolino TTL 1
004 Dispense (normal) [1]
Titrant
Concentration
Volume
Dosing rate
Condition
Acetic acid
2 mol/L
20 mL
60.0 mL/min
No
005 Stir
Speed
Duration
Condition
006 Titration (EQP) [1]
Titrant
Titrant
Concentration
Sensor
Type
Sensor
Unit
Temperature acquisition
Temperature measurement
Stir
Speed
Predispense
Mode
Volume
Wait time
Control
Control
Titrant addition
dE (set value)
dV (min)
dV (max)
Mode
dE
dt
t (min)
t (max)
Evaluation and recognition
Procedure
Threshold
Tendency
Ranges
Add. EQP criteria
Termination
At Vmax
At potential
At slope
After number of
recognized EQPs
Number of EQPs
Combined termination
criteria
Accompanying stating
Accompanying stating
Condition
Condition
METTLER TOLEDO
30%
10 s
No
Na2S2O3
0.1 mol/L
007 Calculation R1
Result
Result unit
Formula
Constant
M
z
Decimal places
Result limits
Record statistics
Extra statistical func.
Send to buffer
Condition
Consumption
mmol
R1=Q
C=1
M[None]
z[None]
4
No
Yes
No
No
No
008 End of sample
009 Blank
Name
Value B =
Unit
Limits
Condition
Back Value ophosphite
Mean[R1]
mmol
No
No
010 Calculation R2
Result
Result unit
Formula
Constant C =
M
z
Decimal places
Result limits
Record statistics
Send to buffer
Condition
Mean Back Value
mmol
R2=Mean[R1]
1
M[None]
z[None]
4
No
Yes
No
No
mV
DM140-SC
mV
No
30%
Volume
15 mL
10 s
User
Dynamic
0.5 mV
0.1 mL
1.5 mL
Equilibrium controlled
1.0 mV
3 s
3 s
30 s
Standard
150
None
0
No
30
No
No
Yes
1
No
No
No
Page 5 of 5
Titration Application M067
METTLER TOLEDO
Literature
1.
"Electrochemistry of semiconductors and Electronics: Processes and Devices",
Eds. John McHardy and Frank Ludwig,
Noyes Publications, Park Ridge, New Jersey (USA) 1992 (ISBN 0-8155-1301-1).
2.
Kenneth E. Langford, Janet Parker,
"Analysis of electroplating and related solutions",
4th Edition, Robert Draper Ltd, Teddington (UK), 1971 (ISBN 0-8521-8033-0).
3.
Peter Wolfram Wild,
"Modern Analysis for Electroplating",
Hampton Hill Finishing Publications, 1974.
METTLER TOLEDO
Electroplating Industry
This application bulletin represents selected, possible application examples.
These have been tested with all possible care in our lab with the analytical
instrument mentioned in the bulletin. The experiments were conducted and the
resulting data evaluated based on our current state of knowledge.
However, the application bulletin does not absolve you from personally testing
its suitability for your intended methods, instruments and purposes. As the use
and transfer of an application example are beyond our control, we cannot
accept responsibility therefore.
When chemicals and solvents are used, the general safety rules
and the directions of the producer must be observed.
Titration Applications Brochure 4
Selected Applications in The Electroplating Industry Periodic check and
exact knowledge of the concentration in an electroplating bath are a
crucial issue to achieve an efficient and optimum plating treatment.
Titration Applications Brochure No. 4 is a collection of representative
methods for the concentration determination of several components in
copper and nickel plating baths.
METTLER TOLEDO offers you a variety solutions for automated titration
analyses in the electroplating industry.
T50A Terminal
T70 with Terminal and
two additional dosing units
www.mt.com
For more information
Mettler-Toledo AG, Analytical
CH-8603 Schwerzenbach, Switzerland
Tel. +41 44 806 77 11
Fax+41 44 806 72 40
Subject to technical changes
© 04/2013 Mettler-Toledo AG, 724561A
Market Support Group AnaChem