Acidity evaluation by acid-base titration

The aim of the work:

Evaluating the acidity by acid-base titration of some solutions used for

soldering in electronics.
Introduction:
In electronics, the reliability of solder joints is influenced not only by the solder material
itself, method of soldering, or possible after cleaning process, but also by the flux properties.
Soldering flux has a major influence on the process of soldering. Upon contact solder alloy with
the surface of copper (tin, aluminium or silver), a stripping action of metal surface occurs. Solder
flux role is to eliminate impurities appearing on metal surface and the formation of a protective
layer. Thus, the solder alloy molecules can give a chemical reaction with the metal (copper,
aluminium or silver) and can form a bond with the metal surface.
For a better adhesion, the surfaces to be bonded must be free of oxides, dust and dirt. If the
removal of the dirt and dust can be easily done by cleaning or can be prevented using proper
storage techniques, thin oxide layer formed on the metal surface it is not so easy. For a solid and
continues bonding, this thin oxide layer is removed during soldering using solder flux. Solder flux
removes oxides and keeps them in suspension and does not allow formation of other oxides during
the soldering operation.
There are two important specifications for soldering fluxes used in electronics: ANSI /
IPC-SF818 and MIL-F-14256. As specified in ANSI / IPC-SF818, fluxes fall into three categories:
Class 1 - consumer products; Class 2 - general industrial and Class 3 - products with high reliability
and military electronics.
Soldering fluxes (Fig. 1) can be classified according to the components and their action
into 4 types:
inorganic fluxes;
organic fluxes;
rosin fluxes;
fluxes that do not need any cleaning after soldering because they are not producing corrosive
residues.

Figure 1. Types of solder fluxes used in electronics

At the beginning there where used only Rosin based fluxes. They are made from a rosin
which is extracted from pine sap, refined and purified. Rosin flux is aciding when liquid, but when
it cools, it become solid and inert. Since rosin flux is inert when solid, it can be left on a circuit
board without harming the circuit, unless the circuit will warm to the point where the rosin may
become liquid and start etching the connection. For this reason it is always a good policy to remove
rosin flux residue. Flux residue can be removed with water or other solvents (like alcohol).
Organic acid fluxes are stronger than the rosin fluxes (clean faster the oxides) but they are
weaker than inorganic fluxes. These fluxes containing weak acids such as citric (C6H8O7), lactic
(C3H6O3), and stearic acid (C18H36O2). Weak organic acids are mixed with solvents such as
isopropyl alcohol and water. Fluxes based on organic acids satisfy the requirements of military
and commercial use. The resulted organic flux residues are water soluble. They have to be removed
as they are electrically conductive, with a potentially important impact on the operation and
performance of a circuit.
Inorganic fluxes are typically a blend based on a strong acid [hydrocloric acid (HCl)], zinc
chloride (ZnCl2), and ammonium chloride (NH4Cl). Generally, they are used for soldering metals
such as copper, brass or stainless steel and not for electronic or electrical works.
The choose of the right solder for electronics is done according to specifications (such as
ANSI/IPC-SF-818 or MIL-F-14256E), and taking into account the following considerations:
 board type: such as single or double sided, multi-layered
 method of components mounting
 solderability of metals to be joined
 material compatibility with solder flux
 soldering method
 acid value
The acid value of soldering flux is important not only for commercial use but also for the
industry. In the electronic components manufacturing process, the evaluation of the acid value of
the flux is necessary. In the manufacture of continuous-flow, the flux acidity is controlled in order
to establish when the soldering flux should be replaced.
Generally, by titration is quantified the concentration of an acid when it is neutralized with
a base of known concentration. In this case the method is called acid-base titration and is based on
the neutralization reaction between an acid and a base, forming salt and water. The method is also
used to determine the acid value of a solution extracted from solder fluxes, by neutralization with
a base in the presence of indicator.
In common laboratory practice, for detecting the equivalence point (to signal the end of the
reaction when acid is neutralized) acid – base indicator is used. Indicator is an acid-base solution
like: phenolphthalein, litmus methyl orange etc. These acid-base indicators are organic compounds
with weak acid or weak basic character, which change their colour with the pH change. The color
change of the acid-base indicators is due to the change in the structure of their molecules,
depending on the depending on acidic or basic nature of the solution.
pH is the decimal logarithm of the opposite sign of the hydrogen ion concentration taken
with the opposite sign and can range between 0-14 (Fig. 2).
 
pH   lg H 

Figure 2. The pH of the solutions

A neutralization reaction between an acid and a base can be generally written as:
 The indicators generally used for such neutralization reactions are shown in Table 1, and
their colour changes are shown in Figure 3.

Table 1. Acid-base indicators

Range of Solution type

Indicator Color change
colour change [0,1%]

 Litmus red - blue 5,5 – 8,3 aqueous solution

 Methyl orange red - yellow 3,1 – 4,4 aqueous solution

 Phenolphthalein colourless – red; pink 8,2 - 10 alcoholic solution

 Metil red red - yellow 4,4 – 6,2 aqueous solution

 Bromthymol blue
yellow - blue 6,0 – 7,6 aqueous solution

Figure 3. pH range of colour change

 The evaluation of the acid value for solder fluxes used in electronics industry will be
performede according to IPC-TM-650 2.3.13, by visual titration.

Apparatus and substances (Fig. 4):

- Automatic Titration System "Titronic"
- Erlenmeyer flask;
- Beaker
- Magnetic stirrer, magnet and magnetic rod;
- Liquid solder flux 1;
- Liquid solder flux 2;
- 0.1 M NaOH solution;
- Phenolphthalein solution;

Figure 4. Experimental set-up for acid-base visual titration

Instructions:

1. In an Erlenmeyer flask (washed and rinsed with distilled water), add using burette the volume
of sample to be analysed (i.e. flux 1 or 2), indicated by the professor;
2. Add distilled water;
3. Add 2-3 drops of indicator - phenolphthalein;
4. Turn on usingthe automatic titration system ON/OFF button;
5. Press the <MODE> button until the display reads <MODE>: TITR. 0.00 mL and start the
titration by pressing the START button;
Initially, the colour indicator in the sample solution to be analysed (flux 1 / flux 2) is colourless.
With the addition of the base, the solution colour turn pink and then red. The titration is stoped
when the pink colour persists for 30 seconds. As soon as the solution is pink, the agitation is
stopped and the Erlenmeyer flask is removed from the magnetic stirrer.
Wash the tip of the automatic titration system with a distilled water jet having a beaker at the
bottom;
6. Read the display base volume used for titration;
7. Return to 0.00 mL by pressing the left mouse button;
Each student should perform at least one titration.
 Results and calculations:

• Fill the following table:

No. Vsolderflux analized CM NaOH VNaOH V NaOH Acid value

[mL] [mL] [mL] [mg NaOH/g of non-
volatile matter]
1 0,1 M
2 0,1 M
3 0,1 M
4 0,1 M
5 0,1 M
6 0,1 M

Assuming that the samples acid analysed were extracted from a quantity of m [g] soldering
flux used in electronics, which contain a percentage of the nonvolatile matter S 85%, the acidity
of the analysed solution is according to IPC-TM-650evaluated as following:

40  V NaOH  CM NaOH
A
m S

Where:
Vsolder flux analysed  volume of solder flux analysed [mL]
CM NaOH - concentration of the solution is titrated with NaOH [M]
VNaOH - the volume of the NaOH solution used in the titration [mL]
V NaOH - Arithmetic mean of the volume of NaOH used for titration [mL]
m - mass flux [g]
S - the percentage of nonvolatile matter - assumed 85%
A - acidity [mg NaOH / g non-volatile matter]

The report will contain compulsory the acid value calculations (do not forget measuring
units!), data tables filled and answers to questions.

Questions:

1. Considering that the mass flux taken for analysis was 1 g and knowing that the flux has to be
changed if the acid value of a flux is greater than or equal to 40 mg NaOH / g nonvolatile matter;
comment your results.

2. What role plays phenolphthalein in an acid-base titration?