On controlling pH
O.L.R. Jacobs, MA, PhD
W.A. Badran, BSc, MSc, DPhil
C.G. Proudfoot, BA, DPhil, CEng, MIEE
C. While, BSc(Eng), PhD, CEng, MIEE
Indexing terms: Process control, Control theory, Computer-aided design
Abstract: The paper summarises a recent investi-
gation to find out what contribution could be
made to pH regulation by modern algorithms for
online estimation and/or adaptive control. Topics
discussed include a mathematical model to
account for nonlinearity; full-scale trials using self-
tuning controllers; a specially developed nonlinear
estimator; use of resulting estimates to drive a
suboptimal 'cautious' control law; and a special-
purpose CAD package. It is concluded that pH
regulation is amenable to good engineering prac-
tice, and that whether or not this should include
modern algorithms is a problem-specific question
which can be answered using the CAD package.
1 Introduction
pH control is notoriously troublesome. It involves non-
linearities and uncertainties which can be so severe that
classical linear feedback does not always achieve satisfac-
tory performance. This paper summarises results of a
recent investigation to find out what contribution could
be made to pH regulation by modern algorithms for
online estimation and/or adaptive control. The investiga-
tion was in the form of a collaborative project combining
academic expertise at Oxford, with facilities for extended
full-scale experimental work at ICI.
Literature on pH is referenced in recent doctoral
theses [e.g. 1-3]. It includes two books [4, 5] giving a
clear account of the subject from the viewpoint of clas-
sical control engineering. One conclusion, confirmed in
our investigation, is that pH control is amenable to good
engineering practice, in such matters as plant layout,
sizing, instrumentation and instrument maintenance. An
important factor is the expectations of plant personnel;
poor performance seems sometimes to occur for no better
reason than that it is expected.
Whether or not good practice need include anything
beyond classical methods is a question whose answer is
problem-specific. This paper discusses some of the deter-
mining factors. Potential contributions from more
Paper 5284D (C8, C9) received 6th January 1986
Dr. Jacobs is with the Department of Engineering Science, University of
Oxford, Parks Road, Oxford 0X1 3PJ, United Kingdom
Dr. Badran is with APV Automation Ltd., Manor Royal, Crawley,
Sussex RH10 2QB, United Kingdom
Dr. Proudfoot is with Unilever Research, Port Sunlight Lab, Mersey-
side L63 2JW, United Kingdom
Dr. While is with ICI PLC, Engineering Department, Runcorn,
Cheshire WA7 4QG, United Kingdom
196
modern methodology are summarised, including a CAD
package which can be used to assess needs of specific
problems.
Discussion is primarily in terms of pH regulation in
processes which can be represented by the continuous
stirred-tank reactor (CSTR) of Fig. 1, where an influent
feedback
y
Fig. 1 pH control in CSTR
stream of variable acidity and flow rate is neutralised by
mixing with concentrated reagent. A feedback signal in
the form of measured pH of effluent drives the controller
which adjusts reagent flow rate. Feedforward signals
measuring influent acidity and flow rate may be available
in some applications. Dynamics of the CSTR have trans-
fer function of the form
1 + S7;
with time constant Ti mainly due to mixing, and dis-
tance-velocity lag T2 mainly due to pipe flows. Inline
static mixing processes can be represented as CSTR with
Tx 4 T2. Tx is proportional to reactor volume and can be
an interesting design parameter: large values have the
good effect of smoothing out disturbances, but the bad
effect of requiring large, and consequently expensive,
plant. T2 has the bad effect that it destabilises feedback
control, and has no good effects.
Two full-scale CSTR were allocated to our investiga-
tion. They were interfaced, one at a time, to a dedicated
PCP11/34 computer which was programmed in Fortran
to perform online data acquisition and storage, as well as
implementing algorithms for real-time estimation and
control [2]. Work on the first CSTR, plant A, had by
1979 led to the general conclusion that 'modern control
technology can contribute substantially to pH control'
[6]. Subsequent work on plant B, a waste brine neutral-
isation vessel, included more detailed investigation of
IEE PROCEEDINGS, Vol. 134, Pt. D, No. 3, MAY 1987
what can be achieved by certain modern algorithms, as Such models underpinned most of our work. They
summarised here. Some dozen other full-scale CSTR were used to create lifelike simulations of full-scale plant
plants were also surveyed [2]. for developing acceptable control algorithms, and for the
Results and conclusions from our investigations
should be generally applicable to other pH control pro-
cesses not exactly conforming to Fig. 1.
Investigated applications of modern methodology are
summarised in the following five Sections of this paper.
Section 2 outlines use of a new variable, ionic concentra-
tion difference [7], to establish mathematical models
which conveniently and explicitly separate two different
factors causing nonlinearity in pH systems. Section 3 is
about our experiences using self-tuning controllers on
full-scale pH plant. Section 4 refers to a novel nonlinear
estimation which could be implemented in an online
computer to generate real-time estimates of unmeasured
plant variables. These estimates could help to determine
control action as discussed in Section 5, which also refers
-1
to a novel 'cautious' [8] control law for pH. Section 6
describes a computer-aided-design (CAD) package which -0.1 0.1
simulates the features of the preceding Sections and can
be used to answer design questions about specific plant, Fig. 2 Nonlinearity in the definition ofpH
including the question of whether classical methods will
be adequate.

2 Mathematical model of pH nonlinearity

One of the principal reasons why pH control is trouble-
some is that controlled processes have the severely non-
linear static characteristics of titration curves. Two
separate factors contribute to this nonlinearity. One is
the known logarithmic nonlinearity in the definition of
pH
+ 0.1
PH=-log10[H ] (1)
The other is the less nonlinear, but often more uncertain,
effect of reaction chemistry, which determines how
hydrogen ion concentration [ H + ] depends on composi-
tions and amounts of reagents.
We found that these two factors can usefully be
separated by taking as the primary variable to represent
acidity, not [ H + ] , but the ionic concentration difference
[7] X defined by
X = [OH-]-[H+] (2)
Fig. 2, obtained by combining eqns. 1 and 2 with the
dissociation equation
[ H + ] [ O H " ] = constant (3)
shows how pH is related to X by the familiar S-shaped
titration curve of strong reagents. When reagents are
strong, the chemistry can be approximated [9] by
X = X, + X (4)
where Xt, XR, Vt and VR are ionic concentration differ-
ences and volumes of influent and reagent, respectively.
When reagents are weak, or 'buffered', the chemistry
gives rise to component-specific nonlinearities which may
have significant effects on control performance or con-
troller design. These nonlinearities can be revealed by
using the inverse of Fig. 2 to strip the known logarithmic
nonlinearity of pH measurement away from an experi-
mental titration curve. Fig. 3 illustrates some typical
results in terms of dimensionless variables {X — Xj)/XR
and VJJVJ. It is the linearity of this representation of eqn.
4 which makes ionic concentration difference X particu-
larly suitable for use as the primary variable in mathe-
matical models.
IEE PROCEEDINGS, Vol. 134, Pt. D, No. 3, MAY 1987
0.1 0.2 0.3
Fig. 3 Examples of nonlinearity due to chemistry
a Effluent 1
b Effluent 2
c Strong acid
d Weak acid
CAD package. They also provided the starting point for
model-based estimation and control, as described in Sec-
tions 4 and 5.
3 Self-tuning controllers
Our work with self-tuning controllers contributes to the
repertoire of thorough studies of full-scale industrial
applications of adaptive control. We confirmed the
general conclusion that if a controlled process can be
satisfactorily controlled by some fixed-parameter linear
controller, then a self-tuning algorithm can achieve the
satisfactory performance and maintain it much more reli-
ably than can be done with hand-tuned conventional
control. The principal condition for satisfactory per-
formance to be so achievable is that the controlled
process be not severely nonlinear.
pH systems can be not severely nonlinear, when they
are required to operate about points where the titration
curve is fiat. This can happen for either or both of two
reasons:
(i) the required operating point may be well away from
the neutral point, where severe nonlinearity mostly arises
197
 (ii) buffering may be present to such an extent that
nonlinearities in the chemistry are severe and cancel out
those of the pH measurement.
The waste brine process of plant B operated in such a
near-linear region: after our extended self-tuning trials,
the plant manager reported that his neutralisation plant
had been held from 0.5 to 1 pH nearer to neutrality,
resulting in considerable saving of reagent and money.
Simulations of plant A, which had little buffering and was
therefore severely nonlinear, confirmed that, although
self-tuning might be preferable to hand-tuning, it could
not of itself achieve good performance about difficult
operating points.
The method of investigation was to establish a lifelike
simulation of the plant and to tune the self-tuners to give
good simulated performance before transferring them to
the real plant. The simulations were done offline in a
VAX computer, using Fortran as in the online computer,
so that source code for the online algorithms might be
directly transferrable.
A key step in obtaining agreement that simulations
were lifelike was the use of a recorded typical time
history of influent flow rate as a simulated plant dis-
turbance.
Three types of self-tuner were investigated [2, 10]: a
novel self-tuning PID algorithm [11], generalised k-
incremental and explicit pole-placement. The pole-
placement algorithm needed more computing power than
the other two implicit algorithms, but gave better per-
formance because it could handle the uncertain time
delays caused by fluctuating flow rate through the neu-
tralisation process. There was little to choose between
the, still satisfactory, performances of the other two
algorithms: dynamics of the controlled process were suffi-
ciently simple that they could be well matched by the
PID controller, and so there was little need for the poten-
tial sophistications of the other more general algorithm.
Figs. 4 and 5 show how the self-tuning PI algorithm
improves on performance of a classical hand-tuned PI
-10
Fig. 4 Waste brine neutralisation under classical PI control
a RMS error = 0.343, b RMS error = 0.337
a Real plant data
b CAD simulation
198
controller. Each Figure shows two pairs of graphs, one
obtained from simulation and the other from the real
waste brine plant. The records are of regulated pH, with
10
20
lOo
o
24 h
Fig. 5 Waste brine neutralisation under self-tuning PI control
a RMS error = 0.059, b RMS error = 0.070
a CAD simulation
b Real plant data
set point 8.5, and of reagent (NaOH) flow which tracks
changes in the effluent load for neutralisation. The step
up in reagent flow shortly after half-time shows that all
cases were subject to similar, major, load disturbances. It
can be seen that the self-tuning controller reduces RMS
error by a factor of five, from about 0.33 to about 0.07
units of pH.
4 Special nonlinear estimators
Good control, whether of pH or any other quantity,
requires good information about exogenous variables
affecting a controlled process, and about its current inter-
nal state. In pH systems such as Fig. 1 the exogenous
variables are usually flow rate and concentration of the
influent stream, and the internal state is characterised by
the ionic concentration difference X. These are variables
whose values can be quite uncertain in practice, partly
because instrumentation for the influent quantities is
often not installed, and partly because the pH measure-
ment of internal state is highly nonlinear and subject to
random errors as well as to systematic biases. We investi-
gated possible ways of using statistical estimation algo-
rithms to extract the required information from available
measurements.
Two types of algorithm were investigated: an online
implementation of Bayes' rule to handle the severe pH
nonlinearity [12], and an extended Kalman filter to esti-
mate the influent variables [1]. A novel linearisation was
developed to couple the first algorithm to the second
[13]. It was found that the Bayes' algorithm would be
well worth implementing if there were significant random
errors in pH measurement, and that the extended
Kalman filter would give valuable information about
influent variables, provided that the titration curve was
known and there was no unknown bias on the pH mea-
surement. Furthermore, it would be possible to estimate
IEE PROCEEDINGS, Vol. 134, Pt. D, No. 3, MAY 1987
and, hence, eliminate such a bias if measurements were
available of the influent variables. Observability prob-
lems prevent simultaneous estimation of influent vari-
ables and of bias.
If the pH measurement is free of significant errors, it
becomes practicable to obtain the internal ionic concen-
tration by inverting the known pH nonlinearity, without
using any statistical estimation. Such inversion can
provide a linearisation of the titration characteristic,
which is adequate for purposes of feedback control when
the chemistry is close to that of strong reagents [14].
The above conclusions are based on simulation
results, because the waste brine process had no influent
instrumentation and its pH measurement was subject to
bias. It therefore had the above-mentioned observability
problems, and was not amenable to statistical estima-
tions.
5 Control algorithms
Simulations showed that, in pH control systems where
statistical estimators can be expected to work, the
resulting estimates could provide a useful basis for
control action. In particular, synthetic feedforward based
on estimates of influent variables, or corrections to feed-
back based on estimates of bias, could sometimes lead to
dramatic improvements in control performance.
Table 1 summarises simulation results showing the
Table 1: simulated RMS errors in pH under self-tuning PI
feedback control
Plant A Plant B
Feedback only 0.164 0.053
Feedback plus synthetic feedforward 0.072 0.053
Feedback plus real feedforward 0.066 0.048
effect of RMS error in plants A and B of synthetic feed-
forward with simultaneous feedback control in the form
of self-tuning PI. For each plant, the set point was at a
typical non-neutral value. In plant A, most of the per-
formance improvement which could have been achieved
by installing real feedforward instrumentation (reduction
of RMS error from 0.164 to 0.066, a factor of about 2.5) is
obtained by using the synthetic feedforward (which
reduces RMS error to 0.072). Plant B was buffered and
operating in a near-linear region, where there was little
need for real feedforward and no improvement to be
obtained by using synthetic feedforward. As the set points
move towards neutrality, both plants were found to
become progressively harder to control: the next stage
after Table 1 was that plant A needed real feedforward
and plant B needed some feedforward.
At a more theoretical level, the question arises of how
to account for interaction between uncertainty about the
current value of internal state X and the nonlinearity
pH(X) of Fig. 2. An early view of this interaction was the
observation [15] that uncertainty about internal state
sets a limit to how close pH can be regulated toward
neutrality.
The interaction can be further discussed by supposing
the value of X to be described by a normal probability
distribution, having mean value Xx and standard devi-
ation a such as might appear from the statistical estima-
tion of the preceding Section. Two consequences of the
nonlinearity are:
(a) the corresponding expected value of pH(X) is not
J (unless Xt = 0)
IEE PROCEEDINGS, Vol. 134, Pt. D, No. 3, MAY 1987
(b) the corresponding mean square error E [(pH0
— pH(X))2] between pH(X) and a set point pH 0 depends
on both Xl and a, and is not generally minimised by
Xx = Xo (unless a = 0), where Xo is the internal state
corresponding to pH 0 .
For given set point pH0 and standard deviation a, the
value of Xt which does minimise mean square error in
pH was determined numerically [1]. The results are sum-
marised in Fig. 6, which shows how the internal state Xx
P H 0 =10
10
Fig. 6 Suboptimal control with caution
to be aimed at by the controller depends on pH 0 and also
on a. When accuracy is good (small a), Xx is the value
Xo of ionic concentration difference corresponding to
pH 0 . As accuracy becomes bad (large a), Xx increases
away from neutrality and can be written
Xt ~ Xo + caution (5)
where the 'caution' [8], which grows with <r, is just what
would be observed in the behaviour of an experienced
plant operator, who moves the set point away from neu-
trality as the process becomes difficult to control.
The above conclusions are based on simulation results
only. The waste brine process of plant B, as well as being
unsuitable for statistical estimations, was well buffered
and could be satisfactorily controlled by linear control-
lers which ignored the titration nonlinearity.
6 CAO package
Nonlinearities and uncertainties in pH systems are
usually so many and strong that controllers cannot be
designed by analysis alone, but must be developed using
a problem-specific simulation. A suitable CAD package
has been produced which uses the mathematical model of
Section 2 as a basis for simulating pH regulation in
CSTR conforming to Fig. 1. All problem-specific features
(e.g. parameter values, noise variances, disturbance time
histories, titration curve) can be specified by the user and
stored. A selection of conventional and modern algo-
rithms for classical control, adaptive control and sta-
tistical estimation, including all the algorithms mentioned
above, is simulated. Performances under the various
algorithms can be compared and the likely return on
their implementation costs can be assessed. The simula-
tion is sufficiently accurate in detail, and well provided
with interactive features, that it can be used to design real
plant. It can be applied in two different ways:
(i) to design controllers for existing plant
(ii) to explore control aspects of proposed new plant.
The package and its applications are more fully described
elsewhere [1, 16, 17]. It was used for the simulations
reported here.
199
 This package is written in Fortran 77 with
(documented) source code of about 10000 lines. It con-
sists of linked modules which use about 400 kbytes of
virtual memory, mainly for storing simulated time his-
tories. Two implementations are available from the
authors, one to run on a VAX and one to run on an IBM
PC.
7 Conclusions
pH control is amenable to good control engineering
practice. Good practice can relate to operation of existing
plant or to designs of new plant. For existing plant it
includes maintenance of accurate pH measurements,
accurate control of reagent flow, exploitation of feed-
forward signals, linearisation to eliminate known nonlin-
earities, use of self-tuning controllers, use of more
complex 'modern' algorithms if suitable data is available.
Inexpensive online computers can be used to implement
the foregoing prescriptions. For designs of new plant,
good control engineering practice also influences choice
of system layout, sizing of mixing vessels and piping, pro-
vision and location and maintenance schedules of valves
and measuring instruments.
A major determinant of performance is the expecta-
tions of plant operators and management, which may
sometimes be unduly pessimistic. Given the will to
achieve good pH control, it should be emphasised that
the modern algorithms which we investigated are not a
substitute for standard good engineering practice, but
can sometimes offer possibilities for further improve-
ments in performance.
Even with good practice there is a limit to how close
pH can be regulated toward neutrality in any one mixing
stage. This limit depends on such factors as the titration
chemistry, the availability and quality of online measure-
ments, the magnitude and rate of disturbances. It may
vary from plant to plant and can usually only be deter-
mined by simulation or experiment. Some existing plants
may operate far from their limit. The CAD package pro-
vides a tool for predicting performance limits in specific
cases, and, thus, for setting realistic expectations about
performance. It can be used to design controllers for
existing plant and, also, to influence the layout and sizing
of proposed new plant.
One difficult feature of some pH problems, which has
not been investigated, is uncertainty about the titration
200
curve of reagent against plant influent. This arises in such
applications as neutralisation of effluent from a large site,
where many different waste streams may contribute to
the final effluent. How to cope with it could be a subject
for further research.
8 Acknowledgment
The collaborative project was supported by SERC grant
GR/A/90093.
9 References
1 BADRAN, W.A.: 'On designing algorithms for controlling pH'.
DPhil thesis, University of Oxford, 1984
2 PROUDFOOT, C.G.: 'Industrial implementation of on-line com-
puter control of pH\ DPhil thesis, University of Oxford, 1983
3 GUSTAFSSON, T.K.: 'A study of modelling and control of pH\
Doctoral thesis, Report 84-4, Abo Akademi, 1984
4 SHINSKEY, F.G.: 'pH and pION control' (Wiley, 1973)
5 MOORE, R.L.: 'Neutralisation of waste water by pH control'
(Instrument Society of America, 1978)
6 JACOBS, O.L.R., HEWKIN, P.F., and WHILE, G: 'Online com-
puter control of pH in an industrial process', IEE Proc. D, Control
Theory & Appi, 1980,127, (4), pp. 161-168
7 ORAVA, P.J., and NEIMI, A.J.: 'State model and stability analysis
of a pH control process', Int. J. Control, 1974, 20, pp. 557-567
8 JACOBS, O.L.R., and PATCHELL, J.W.: 'Caution and probing in
stochastic control', ibid., 1972,16, pp. 189-199
9 JACOBS, O.L.R.: 'pH regulation' 'Encyclopaedia of systems and
control' (Pergamon, 1987)
10 PROUDFOOT, C.G., CLARKE, D.W., JACOBS, O.L.R., and
TUFFS, P.S.: 'Comparative study of self-tuning controllers regulat-
ing pH in an industrial process'. IEE Conf. Publ. 252, 1985, Vol. 2,
pp. 359-364
11 PROUDFOOT, C.G., GAWTHROP, P.J., and JACOBS, O.L.R.:
'Self-tuning PI control of a pH neutralisation process', IEE Proc. D,
Control Theory & Appi, 1983,130, (5), pp. 267-272
12 JACOBS, O.L.R., and BRIGGS, M.S.: 'Monte Carlo comparisons
of estimators for pH nonlinearity', Trans. Inst. Meas. & Control,
1984,6, (6), pp. 287-292
13 JACOBS, O.L.R.: 'Recursive estimation for nonlinear Wiener
systems by online implementation of Bayes' rule', ibid., 1986, 7, (5),
pp. 245-250
14 ROBERTS, P.D.: 'Non-linear control of a neutralisation process',
Meas. & Control 1971, 4, pp. T151-T157
15 HEWKIN, P.F.: 'The control of pH using modern algorithms and
online computers'. D.Phil, thesis, University of Oxford, 1979
16 JACOBS, O.L.R., and BADRAN, W.A.: 'A computer package for
designing pH regulation systems'. Oxford University Engineering
Lab. Report 1506/3, 1983
17 JACOBS, O.L.R., and BADRAN, W.A.: 'CAD of pH control
systems'. 9th IFAC congress, Budapest, paper 11.2/D/2, 1984
IEE PROCEEDINGS, Vol. 134, Pt. D, No. 3, MAY 1987