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MÉTODOS ELÉCTRICOS

Objetivos :

a)Recordar los conocimientos previos de potenciales REDOX.

b)Conocer la construcción y las limitaciones industriales de los diferentes métodos y
sensores eléctricos.

1.- Potenciometrías.
Electrodos Indicadores :
a) Primera especie.
b) segunda especie
c) Redox.

2.- Electrodos de membrana.

a) Electrodo de vidrio. Medida de pH y pM.
b) Electrodos de Membrana líquida, cristalina y de gases.

3.- Criterios de selección de electrodos. Características.

4.- Uso industrial de electrodos.

5.- Culombimetrías.

6.- Conductimetrías.

7.- Voltamperometrías.

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Métodos eléctricos
Potenciometrías, Culombimetrías, Conductimetrías. Voltamperometrías.

Introducción

Son métodos en los que se miden una o más variables eléctricas: Potencial, cantidad de corriente,
resistencia, …

1.- Potenciometrías.

Las reacciones redox son todas aquellas reacciones en las que existe una transferencia de electrones.
Un ejemplo es:

Fe2+ + Ce4+
Fe3+ + Ce3+

En toda reacción redox existe un oxidante y un reductor. El oxidante es una sustancia con gran
afinidad a los electrones, y el reductor otra sustancia que los cede fácilmente.

Del ejemplo: Ce4+: Oxidante, porque oxida y él se reduce.

Fe2+: Reductor, reduce y se oxida.

La tendencia a reducirse de los distintos elementos o especies está cuantificada por lo que se
denomina potencial estandard. Estos potenciales estandard están tabulados en lo que se denomina
serie electroquímica.

Los semisistemas que tienen potenciales estandard elevados son oxidantes y viceversa. En general,
el potencial desarrollado por un semisistema viene cuantificado por lo que se conoce como ecuación
de Nerst, que dice que:

Eox/red = E0ox/red – RT/nF Ln ([ox]/[Red])

Donde R es la cte de los gases = 8,316 J K mol-1 ; n = nº de e- que intercambia ; F = 96487

Culombios.

Si pasamos el Ln (neperiano) a Log (decimal) nos quedaría la expresión:

Eox/red = E0ox/red – 0.056/n Log ([ox]/[Red])

Para que de lugar una reacción redox sea espontánea, la constante de equilibrio tiene que ser mayor
que uno, y esto depende de los potenciales que en el sistema actúen como oxidantes y de los que
actúen como reductor. Si la diferencia es positiva la reacción es espontánea y viceversa.

En el ejemplo del hierro con cerio sentido opuesto al propuesto, k= 10-14.2 , por lo que el Fe3+ no
puede oxidar al Ce3+.

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A medida que se desarrolla la reacción, disminuye la [Fe2+] y la [Ce4+ ] , para aumentar las
concentraciones de Fe3+y Ce3+, lo que supone que el potencial desarrollado por Ce4+/Ce3+ diminuye
y el del Fe2+/Fe3+ aumenta. Cuando se igualen se alcanzará el equilibrio.

Las pilas redox se caracterizan porque pueden intervenir en ellas unos reactivos llamados reactivos
electroquímicos o electrodos, que son simplemente un conductor, como puede ser un hilo de
platino. Además del electrodo es necesario una especie en disolución que tenga tendencia a captar o
ceder electrones. Una célula galvánica es aquella en la que una reacción química espontánea genera
tensión eléctrica. Para lograrlo es necesario que uno de los reactivos se oxide y el otro se reduzca.
Es necesario, además, que estos reactivos estén separados físicamente para evitar que los electrones
se transfieran directamente del producto al disolvente y forzar a estos electrones a circular por un
circuito externo para ir de un reactivo a otro. Además, debe existir lo que se denomina puente
salino, para mantener la electroneutralidad.

Donde tiene lugar la reacción recibe el nombre de ánodo, y donde tiene lugar la reducción se llama
cátodo.

Puente salino: Pieza de vidrio en forma de U que contiene un electrolito fuerte, como por ejemplo:
KCl ( K+ + Cl-).

E = Ecátodo - Eánodo - IR (donde R es la resistencia de los iones a moverse en el puente salino).

Con la ecuación de Nerst podemos usar una pila como detector de una especia química cuando
conozcamos las concentraciones de las especies que forman la pila. Ejemplo:

Zn0
Zn2+ + 2 e- Eox/red = E0ox/red – 0.056/2 Log [Zn2+]

Esta pila la vamos a usar para determinar la [Zn2+]. Si somos capaces de mantener constante el
potencial del cátodo, el otro potencial depende sólo de la concentración de Zn2+, luego modificando
su concentración variaremos así el potencial del cátodo y podremos ver la variación de potencial
con relación a la concentración de Zn2+ estableciendo una recta de calibrado; en esto se basa la
potenciometría.

Los métodos potencimétricos necesitan una instrumentación muy sencilla:

• 1 electrodo de referencia.

• 1 electrodo indicador.

• 1 dispositivo para medir el potencial.

Electrodos de referencia

Un buen electrodo de referencia debe presentar un potencial exactamente conocido, constante e

independiente de las variaciones de la concentración de la disolución donde esté sumergido.
Además, debe ser robusto y fácil de preparar.

El primer electrodo de referencia fue el electrodo estándar de H2, el cual es un electrodo de

referencia universal; a partir de él se calcularon los potenciales estándar del resto de los
semisistemas redox para realizar la serie electroquímica. Está constituido por un hilo de platino
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platinizado sumergido en una disolución de H+ (ácido fuerte) con actividad igual a la unidad, y a la
que se le hace burbujear H2 gaseoso a una P= 1 atm y a 25ºC. La actividad es la concentración
efectiva.

½ H2
H+ + e- E0 = 0.00 V

Este electrodo, actualmente se utiliza muy poco ya que es muy difícil de preparar, el hidrógeno es
peligroso (mezclas explosivas) y bastante irreproducible.

El electrodo de colomelanos saturado es mucho más utilizado y se basa en el sistema cloruro

mercurioso/Cl-.

Hg2Cl2(s) + 2 e-
2 Hg(l) + 2 Cl- E025º = 0.2444V

Para mantener un potencial constante se añade KCl saturado. Por problemas ambientales el
electrodo de mercurio está dejándose de utilizar.

Otro electrodo muy utilizado es el de AgCl/Ag, cuyo funcionamiento es similar.

AgCl(s) + e-
Ag(s) + Cl- E025º = 0.199V

Para que sea el potencial cte. hay que añadir KCl.

Potencial de unión liquida:

Surge en el límite de separación de dos disoluciones de electrolito de distinta concentración; si

tenemos una disolución de HCl 0.1 M separado por una barrera de otra de HCl 0.01 M para evitar
que se mezclen, la diferencia de concentración produce la difusión de los protones y de los cloruros
de la disolución más concentrada a la más diluida. Entonces tienden a igualarse las concentraciones.

Debido a la mayor movilidad de los H+ aparece una separación de cargas de forma que el lado de la
membrana que está junto a la disolución más diluida se carga positivamente; el lado que está en la
disolución más concentrada se carga negativamente. Inmediatamente se alcanza un equilibrio al
verse frenados los protones debido a la repulsión de las cargas y dando lugar a un potencial llamado
“de unión líquida”.

Este potencial lo debemos minimizar, y esto se consigue con un puente salino. La eficacia del
puente salino es máxima si el catión y el anión que lo forman tienen igual movilidad y, además, se
encuentra en alta disolución. Un puente salino que cumple este requisito es una disolución de KCl,
reduciéndose el valor del potencial de unión líquida a un valor de milésima de voltio y por lo tanto
despreciable. Por ello, en todos los electrodos de referencia hay un puente salino entre este
electrodo y la disolución que vamos a medir.

Electrodos indicadores

Deben responder de forma rápida y reproducible a los cambios de concentración del analito.
Aunque no existe ningún electrodo absolutamente específico en su respuesta, actualmente sí que
nos encontramos con electrodos altamente selectivos.
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a) Electrodos de 1ª especie ó Metálicos. Se utilizan para cuantificar el catión proveniente del metal
con que está construido el electrodo. Un electrodo de este tipo es un trozo de metal que está en
equilibrio directo con el catión del metal. Para este tipo de electrodos se utiliza Ag, Hg, Pb y Cd.
No todos los metales sirven para construir un electrodo de este tipo, debido a que no desarrollan
potenciales reproducibles.

En general se basa en una reacción de oxidación de un metal:

Ag0
Ag+ + e- Eox/red = E0ox/red – 0.056/1 Log [Ag+]

b) Electrodos de 2ª especie. Son aquellos donde los metales actúan como detectores de aniones que
forman precipitados bastante insolubles o complejos y bastante estables con el catión del metal.

Un ejemplo es el que se utiliza para la determinación de cloruros o para determinar EDTA=Y4-,

importante porque determina muchos cationes y valora la dureza del agua.

c) Inertes para sistemas redox. Metales inertes tales como el Au, Pt, Pd o C(grafito) desarrollan
un potencial que corresponde al potencial del sistema redox con el que están en contacto. Por
ejemplo, si introducimos un hilo de platino en una disolución que contenga Ce4+ y Ce3+ el potencial
del indicador va a ser:

Eox/red = E0ox/red – 0.056/1 Log [Ce4+]/ [Ce3+]

d) Indicadores de membrana: Durante muchos años, el método más cómodo para medir el pH de
una disolución es la medida de un potencial que adquiere una membrana cuando separa dos
disoluciones que contienen distinta concentración de H+.

En la actualidad, existen membranas que son sensibles a una gran variedad de iones. Ninguno de
estos electrodos basan su funcionamiento en fenómenos electroquímicos redox, sino en fenómenos
de intercambio iónico. Un electrodo de membrana, también llamado electrodo selectivo, consiste en
una membrana que responde más o menos selectivamente a un ión y que está en contacto por un
lado con una disolución del ión que queremos cuantificar y por otro lado con una disolución del
mismo ión de actividad conocida, que también está en contacto con un electrodo de referencia.

Una membrana es una capa delgada, generalmente de vidrio, que separa dos disoluciones y que es
permeable o semipermeable a uno de los componentes de las disoluciones con las que está en
contacto. Para medir el potencial de una membrana hay que formar una célula electroquímica con
un electrodo de referencia en cada uno de los lados de la membrana. La modificación del transporte
de materia debido a la presencia de la membrana da lugar a variaciones del potencial electrostático.
Estas variaciones son función de la composición de las disoluciones en que esté en contacto, y se
puede relacionar con las concentraciones de un ión determinado.

Los electrodos selectivos o electrodos de membrana se clasifican atendiendo al estado físico de la

membrana. Así nos encontramos electrodos sólidos o cristalinos, cuyo ejemplo más significativo es
el electrodo de vidrio que sirve para determinar el pH., También tenemos electrodos líquidos,
constituidos por un soporte sólido saturado de especies iónicas o no iónicas y por último electrodos
especiales, donde se encuentran los electrodos para gases, electrodos enzimatizados o biosensores.

Se ha estudiado como influye la composición de la membrana en la sensibilidad del electrodo.

Centrándonos solamente en el electrodo de vidrio, la composición de vidrio más usado es el
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Corning 015, constituidos por 22% Na2O, 6%CaO y 72% SiO2. Este vidrio es bastante sensible a
los H+ para pH inferiores a 9. Para pH superiores empieza a ser También sensible a los iones Na+.
Actualmente se utiliza otro tipo de vidrio donde en mayor o en menor medida se han reemplazado
los Na+ y Ca2+ con Li+ y Ba2+. Parece ser que de esta forma se alcanza mayor selectividad y las
membranas tienen un tiempo de vida más largo.

En el interior del tubo de vidrio hay una disolución de HCl de concentración conocida saturado con
KCl. En este tubo de vidrio también se introduce un hilo de Ag, que junto con los cloruros que hay
en el medio formará un electrodo de referencia AgCl/Ag. Este electrodo estándar de referencia
interior se conectará a un terminal del medidor de potencial. El otro terminal estará unido al otro
electrodo de referencia denominado de calomelanos.

En los huecos se encuentran cationes para contrarrestar la carga negativa de los electrones.

Todos los vidrios han de estar hidratados para poder determinar el pH.

Los vidrios que no son higroscópicos no son sensibles al pH. Los vidrio higroscópicos, si están
deshidratados pierden su sensibilidad, pero este efecto es reversible.

Los iones monovalentes como son el Na+ y el Li+ pueden moverse por los huecos de la red, y estos
son los responsables de que la membrana conduzca la electricidad. Cuando la membrana la
ponemos en contacto con H2O lo que tiene lugar es una reacción de intercambio iónico, de forma
que los protones que están en disolución reemplazan al Na+ del vidrio. Como es un proceso de
difusión iónica en un sólido esta no es instantánea y se necesita un tiempo mínimo para alcanzar el
equilibrio y obtener una respuesta adecuada (15 a 20 segundos para el 95% de la respuesta)

La constante de equilibrio de esta reacción es tan elevada que se puede decir que las superficies
externas de la membrana están constituidas únicamente por ácido silícico.

Para que una membrana de este tipo pueda actuar como electrodo indicador debe conducir la
electricidad. Como hemos dicho, esta conducción se debe a los iones monovalentes, que serán los
H+ y los Na+. Los Na+ serán los portadores de carga en el interior de la membrana en la zona en que
está deshidratada, mientras que en la superficie hidratada los responsables serán los H+, de forma
que los H+ tenderán a moverse en dirección a la disolución más diluida, de forma que la superficie
de la membrana que está en contacto con la disolución más diluida adquirirá carga +, creándose así
el denominado potencial de membrana. La magnitud de este potencial depende de la relación de
concentraciones del ión H+ en las dos disoluciones.

Exterior: V1 = j1 + 0.0591 log (a1/a’2)

Interior: V2 = j2 + 0.0591 log (a2/a’2)

V1 y V2 son los potenciales asociados a cada una de las interfases constituidas por superficie de la
membrana en disolución.

j1 y j2 = ctes. Representan el nº de posiciones disponibles de intercambio.

a1 y a2 = actividades de los H+ en la disolución interior y exterior.

a'1 y a'2 = actividades de H+ en ambas superficies de la membrana (interna y externa).

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Si consideramos que existe el mismo nº de posiciones negativas en la cara interna y externa de la
membrana: j1 = j2

y suponiendo iguales las actividades en la membrana de vidrio: a'1 = a'2

Si a2 es conocida y constante., podemos obtener la siguiente expresión:

V2-V1 = 0.059 log a2/a1 = K + 0.059 pH

Si nosotros ponemos la membrana en contacto con dos disoluciones de concentraciones iguales y

utilizamos dos electrodos de referencia exactamente iguales, el potencial de unión líquida, Eul, es
nulo, pero sin embargo esto no es así, pues siempre hay un potencial que se conoce como potencial
de asimetría y que, además, cambia gradualmente con el tiempo. No se sabe a que es debido, pero lo
más seguro es que se deba a tensiones sufridas en la superficie de la membrana durante la
fabricación de la misma y al desgaste de la superficie externa al ponerse en contacto con diferentes
reactivos.

Análogamente a los electrodos de membrana de vidrio se pueden construir de membrana líquida

(con un compuesto líquido insoluble en el disolvente de la disolución) o de membrana cristalina
(con un precipitado cristalino insoluble del anión o del catión a determinar). La sensibilidad
(pendiente) dependerá de la carga del ión y además las interferencias con otros iones de la
disolución, deben ser tenidas en cuenta.

Errores que se cometen al medir el pH

Error alcalino, que aparece a pH superiores a 9. A partir de ese pH el electrodo se hace también
sensible al y nos da valores de pH inferiores a los reales si la concentración de Na+ es elevada. Se
debe a la competencia de iones Na+ y H+ .

Error ácido, aparece a pH < 1. No se conoce bien su origen, aunque parece ser que al haber una
gran concentración de H+ hay competencia entre ellos y se producen lecturas superiores a las que
nos debían dar.

Errores debidos a deshidratación, una membrana es sensible al pH siempre que esté hidratada. Si
no es así puede dar errores en las medidas.

También se pueden producir errores en la determinación de pH de una disolución no tamponada

próxima a la neutralidad. El equilibrio entre la membrana y este tipo de disoluciones se alcanza
lentamente, y si no se deja bastante tiempo el electrodo con la concentración el resultado obtenido
puede ser erróneo. Es conveniente que el electrodo se haya limpiado bien con agua y que la
disolución se agite cuando se este determinando el pH.

Error debido al potencial de unión líquida de los electrones de referencia: En la constante K' de
la ecuación que nos relaciona el potencial con el pH se incluye el potencial debido al electrodo de
referencia, que decíamos que siempre va a tener un potencial denominado de unión líquida.
Nosotros consideramos que este potencial no varía cuando variamos de la disolución patrón a la
disolución problema, pero esto no es así, porque ya dijimos que el potencial de unión líquida
dependía de la composición de la disolución donde se sumergía el electrodo, y esto va a dar lugar a
un error que puede ser de 0.02 unidades de pH.

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Error debido a una mala interpretación de los patrones, o una modificación de la concentración
de los mismos durante su almacenamiento.

La medida de los potenciales de un electrodo selectivo desarrollados es una manera fácil y cómoda
de cuantificar un ión determinado; si el electrodo es lo suficientemente selectivo, no es necesario
llevar a cabo separaciones previas, tan solo tenemos que realizar un calibrado utilizando patrones de
concentración exactamente conocida de ese ión y después medir el potencial de la disolución
problema. La ecuación que nos relaciona el potencial con la concentración de los cationes es:

V2-V1 = K + 0.059/n pM , donde n ES La carga del ión

En el caso de los cationes la ecuación es:

pM = -log a1 = E0bs-(Eref + Eulíquida)/ (0.06/n) = Eobs – K/ (0.06/n)

En el caso de los aniones la ecuación cambia el signo y es:

pX = -log a1 = E0bs+(Eref + Eulíquida)/ (0.06/n) = Eobs + K/ (0.06/n)

Un error que es inevitable es que ésta constante de proporcionalidad “K”, que la calculamos
mediante un calibrado, puede variar al cambiar la naturaleza de la disolución en que introducimos el
electrodo.

Aparte, existe otro error, y es que todos estos potenciales que medimos son función de las
actividades, y no de las concentraciones. A nosotros generalmente nos pueden medir la
concentración de algo, y por lo tanto deberíamos trabajar utilizando coeficientes de actividad (fa),
pero

Actividad ión= f actividad x [ión]

éstos son muy difíciles de calcular, y dependen de la fuerza iónica de la disolución, que es

µ = ½ ∑[Mi]Zi2

Cuanto mayor es la concentración de electrolitos, mayor es µ.

Para saber ese error, lo que se hace es añadir a los patrones y a la disolución problema una
concentración elevada de un electrolito inerte, de forma que el efecto de los electrolitos de la matriz
del problema sea despreciable frente a esa alta concentración.

Para lo que más se utiliza la potenciometría es para valoraciones potenciométricas, en las que se
mide el potencial de una disolución y se registra en función del volumen de agente valorante
añadido. Las valoraciones potenciométricas dan valores más precisos que las de los indicadores
coloreados. Son muy útiles en la valoración de disoluciones coloreadas o turbias, porque no
podríamos usar indicadores coloreados (no se aprecia el viraje). Son más lentos, aunque son más
fáciles de automatizar. Se Obtiene una curva típica de valoración en la que el punto final coincide
con el punto de inflexión.

No solamente se utiliza para valoraciones ácido-base, sino también para cualquier tipo de
valoraciones. Sólo es necesario seleccionar el electrodo indicador adecuado.
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pH Control: A Magical Mystery Tour

Systems for pH control are characterized by extreme rangeability and sensitivity, and are also subject to difficulties arising
from contact between measuring electrodes and hostile fluids. Case histories of representative installations show that success
in implementing these control systems depends not only on assessing the complexity of the loop and selecting a control
strategy but also on recognizing and avoiding pitfalls while specifying and installing instrumentation, equipment, and piping.

I do not pretend to be the world's champion pH problem solver. But, I have helped rescue over 50 foundering pH control
systems in the past 5 years and am still rational enough to tell you about it. Most people hardly notice that I twitch at the
mention of hydrogen ion concentration.

WHY IT'S A PROBLEM

Why is pH control a problem? After all, you've got an odd but simple scale of measurement from 0 to 14 dimensionless units,
measuring electrodes that have been around long enough to be well understood and readily applied, and instrument vendors
who must have seen every possible application by now.

Rangeability and Sensitivity

One basic source of difficulty is that - as countless articles, technical papers, and textbooks point out - the pH scale
corresponds to hydrogen ion concentrations from 100 to 10-14 moles per liter. No other common measurement covers such a
tremendous range. Another intrinsic constraint is that measuring electrodes can respond to changes as small as 0.001 pH, so
instruments can track hydrogen ion concentration changes as small as 5x10-10 moles per liter at 7 pH. No other common
measurement has such tremendous sensitivity.

The implications of such great rangeability and sensitivity can be illustrated by considering a continuous feedback
neutralization system for a strong acid and a strong base. The reagent flow should essentially be proportional to the difference
between the hydrogen ion concentration of the process fluid and the setpoint. A reagent control valve must therefore have a
rangeability greater than 10,000,000:1 for a setpoint of 7 pH when the incoming stream fluctuates between 0 and 7 pH.
Moreover, uncertainties in the control valve stroke translate directly into pH errors, such that hysteresis of only 0.00005% can
cause an offset of 1 pH for a 7 pH setpoint.

The situation is like playing golf. The distance from the tee to the green represents rangeability and the ratio of the hole
diameter to this distance is analogous to sensitivity. For an application requiring a strong base to neutralize a strong acid or
vice versa, the tee would be about 1,000,000 yards from the green and the hole would be about 3-1/2 inches in diameter. A
hole-in-one is impossible. And using the same size control valve at each stage would be like hiring a gorilla to drive the ball to
the green in one stroke, then finding that it tends to overshoot the hole on the putt.

How is it even possible to control a process under these conditions? Rangeability and sensitivity limitations can be overcome
by approaching the setpoint in stages, using successively smaller control valves with high performance positioners.

The real world

A host of other constraints adds to the difficulties of pH control. These range from the necessity of wetting the electrodes -
with consequent susceptibility to leakage and attack by the fluid, to long delays introduced by the need to mix large volumes
of process material with small amounts of reagent. Even with a good understanding of measurement and control concepts,
these real-world effects introduce an element of magical mystery into pH.

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SOME TYPICAL PROBLEMS
TABLE I.
No pH complications are really
typical. And the systems that The Facts of Life
are easy to implement don't
get referred back to those of
us whom InTech refers to as
1. Instrumentation is frequently the source of disturbance for pH systems, through
repeatability error, measurement noise, or valve hysteresis.
the noodnicks from Central
Engineering. But the
installations I will describe are 2. In-line pH loops will oscillate, regardless of controller modes and tuning, if setpoints
typical of those I have are on the steep parts of the titration curves.
encountered recently, and
illustrate the types of
problems that you can expect. 3. pH electrode submersion assemblies with unencapsulated terminations below the
liquid surface will eventually have wet terminations.
To avoid arguments with our
Legal Department about 4. Reagent control valves that are not close-coupled to the injection point on in-line
proprietary information, I will systems will cause reagent delivery delays large enough to describe the tools of your
not mention any places or trade in words your sister may not even know.
names; I'd even prefer that
you forget my name when you
5. You need either a flowmeter or a seer to diagnose reagent delivery problems.
finish reading. Also, to help
guide you through my 6. Flow feedforward signals should be multiplied by pH controller outputs and employed
tribulations, and those you to operate reagent valves directly or to establish reagent flow control setpoints
will encounter yourselves, I've
prepared Table I, enumerating
what you can think of as the 7. Transportation delays to pH electrodes in analyzer houses will exceed mixing
Facts of Life. Commit this deadlines - such that increasing comfort in checking the electrodes is offset by
Table to memory; you'll be decreasing comfort in checking trend recordings.
quizzed on it in the morning.

8. Injection electrodes should be preferred to sample holder assemblies whenever

Where's the tank? possible to reduce maintenance problems and improve response times - but not all
injection electrodes are created equal.
An application involved a
strong acid waste flow, to be 9. Large tanks are fine if you don't have to control them; use the volume upstream to
neutralized by a strong basic reduce reagent consumption or downstream to reduce control error. If you can't
reagent. It was called in make-up your mind where to use one, put it downstream.
because the pH was swinging
from 0 to 14 despite efforts to
tune the controllers, manually 10. Install one or three but never two electrodes for a pH measurement.
manipulate the reagent, and
regulate the influent flow.
When I got to the plant, I
gazed over the horizon and
didn't see any tanks. I
suddenly realized that I had a
major problem.

Figure 1a shows the original control system. This used a ratio controller to proportion reagent to acid waste flow upstream of
an in-line mixer. A separate pH controller was used in a loop on a sump. The system designers did not realize that the flow
measurement error and the flow control valve hysteresis must both be less than 0.00005% to stay within 1 pH of the 7 pH
setpoint. They assumed that disturbances would be small since the change in waste composition was slow and its flow was
fixed by a controller. The design team did not know Fact of Life #1.

A system involving a strong acid and a strong base normally requires three stages of control to hold a solution within 1 pH of 7
pH (Ref 1). Since cost was stressed as a factor, I kept the existing mixer and sump as one stage and added two vertical well-
mixed tanks downstream for the second and third stages. Further, I agreed to not install controls on the third stage until the
need was demonstrated. The third stage volume therefore served as a filter for the oscillation from the second stage.

For the first stage of control, we started by replacing the ratio flow system with a fast inline pH loop. This received a remote
setpoint from a second pH controller on the sump. The fast in-line loop would initiate the correction and depend on the sump
volume to average out hydrogen ion concentration deviations. Linear control system analysis predicted that this combination
would be as effective as a single well-mixed vertical tank. It didn't work. Dynamic simulation showed that the in-line loop
would oscillate between 0 and 14 pH for all controller settings. A plant test confirmed the result.pH

At first, I thought the sump was somehow not providing the anticipated filtering. Then I remembered Fact of Life #2. The filter
was acting on hydrogen ion concentration, not pH. The sump was attenuating concentration oscillations by a factor of 100, but
is corresponded to a decrease of only 2 pH. Attenuation was improved by reducing the distance from the mixer to the control
valve and electrodes so the oscillation was faster.

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The second state had a notch-gain pH controller was an output that provided a pulse frequency proportional to an analog
signal. Above 25% controller output, the valve was throttled normally; below 25%, valve rangeability was extended using
pulse frequency or interval control.

Figure 1b shows the upgraded installation. This system could keep pH within the desired offset band at the outlet of the third
stage. However, the sump controller was difficult to tune and recovery from startup or waste flow controller setpoint change
was slow.

FIGURE 1. Where's the tank? (a)-unsuccessful and (b)-successful pH control systems for a continuous neutralization process
initially having no mixing tank.

If I were designing this system today, I would place a feedforward loop on the sump and would install controls on the third
stage. I would also characterize the feedforward and feedback signals. The characterization would involve calculating reagent
demand from the pH measurement using the titration curve, and using the result as the control command. This would reduce
nonlinearity, recovery time, sensitivity, and tuning difficulty. Microprocessor-based controllers can provide the necessary
calculation accuracy and ease of implementation.

As with any new system, startup was not without bugs. Some were of the common garden variety - like transposed wires and
incorrectly calibrated positioners. Others were of the magical mystery type peculiar to pH systems.

For example, at high pH levels, the measurement went downscale as the strong base reagent flow increased. As you can
imagine, this drove the control system - and us - kind of crazy. The difficulty turned out to be that the measuring electrodes in
the in-line loop were not specified with high-pH glass. Normally this would cause the measurement to read low by about 1 pH
at the upper end of the scale. In our case, it caused a reversed response. This performance was confirmed by the vendor, and
was corrected by replacing the electrodes with low sodium ion error devices.

Another magical mystery effect was that the electrode response for the well mixed tank became erratic. We found water on
the terminals inside the submersion assembly. The vendor told us if we bought an assembly that cost twice as much, the
leakage would stop. We did; it didn't. The vendor then told us to buy a newly developed assembly, for four times the price of
the original and the leakage would surely stop. Rather than make the same mistake three times, I shopped around and found
a throwaway electrode assembly completely encapsulated in plastic - at half the price of the original. It worked like a charm. A
similar experience with a submersion assembly from another vendor led me to Fact of Life #3.

Where's the valve?

Another application required small quantities of a highly concentrated viscous reagent for continuous neutralization of a waste
stream. The control system was so slow that disturbances passed through the plant long before any corrective action took
effect; further, the pH trend recording had a noise band that far exceeded the allowable setpoint offset. When I inspected the
system, I stood near the injection point at the inlet to the pipeline mixer, scanned the horizon and didn't see any reagent
control valve. I quickly deduced I had a major problem. Figure 2a shows what I found.

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FIGURE 2. Where's the valve? (a)-unsuccessful and (b)-successful pH control systems for a process involving a highly viscous
concentrated reagent.

Can you spot a control problem exclusive of the pH loop in this figure? The sump level controller sets the flow in the upper
outlet branch. The mixer flow controller simultaneously manipulates the valve in the lower branch to keep a constant flow out
of the sump. The system is obviously overcontrolled. We got out of this mess by cascading the level controller output to flow
controller setpoint.

Now for the pH loop. The reagent was being injected into the pipeline under the control of a positive displacement metering
pump. The pump was about 300 feet away from the mixer. This distance caused a delay when the pump was activated -
because process fluid would backfill the injection piping and had to be pushed out of the line before any reagent could be
delivered. It doesn't take much fancy mathematics to figure that at one gallon per hour, it takes an hour to push a gallon
through a pipe. This led to Fact of Life #4. We also found a delay when the speed of the pump changed, but never really
identified the cause. We would have blamed it on air pockets, if there had been any. The answer probably lies in the ketchup
bottle - related to low flow of viscous fluids.

Anyway, we reduced the delays and resulting noise band by an order of magnitude when we replaced the remote metering
pump with a closecoupled control valve. The valve was manipulated using a ratio controller to proportion the reagent flow to
the sump discharge flow, correcting the ratio with the in-line pH loop.

Some noise still remained, due to poor distribution of the injected reagent into the pipeline. This couldn't be eliminated,
because it required making the injection port smaller so the reagent velocity would be larger. Unfortunately, a hole small
enough to do the job was too small to keep from plugging. The noise was more of a nuisance on the trend chart than in the
system, so the record was cleaned up by passing the measurement signal through an electronic filter.

We thought our problems were over, when magical mystery reared its ugly head. As the miniature reagent valve was stroked
from closed to open, the reagent flow measurement momentarily increased and then went to zero. The magnetic flowmeter
was immediately suspect - but came through with a clean bill of health; we checked the wiring and found it to be correct; the
vendor examined and verified the integrity of the electronics; we tested the meter on water and observed that it respond
correctly. We than tried changing valve trim, but several tests yielded the same results.

I was about to throw the tiny but costly trims away, leave the engineering profession, and enter a seminary. During this period
of contemplation, I suddenly noticed what looked to be a reverse taper on the trims. It was hard to tell for sure, because the
parts were small, but I confirmed the observation with a micrometer. In desperation to get home from this startup, I
calculated the contour of the plug for a linear characteristic, made a sketch, and had the parts machined.

The valve worked fine with the homemade trim. The reverse taper had caused the flow to decrease as the stroke increased.
The momentary surge inflow at the start of the stroke was caused by the plug lifting off the seat just enough to provide a
small annular clearance. How did the reverse taper get there in the first place? I never found out for sure, but did learn that
the trims were too small to be standard and were specially machined by the vendor for the order. As far as I was concerned,
they were too special. You can imagine how difficult it would have been to diagnose this valve problem if there was no reagent
flow meter. This leads to Fact of Life #5.

Another instrumentation problem occurred later, when one of the design engineers decided to modify the system and recover
some panel space. He installed a feedforward controller in place of the ratio station and pH-based flow controller. The device
added the flow feedforward signal to the flow command from the pH controller. The vendor, anxious to sell a feedforward
element, thought it was a great idea. In operation, as you should have guessed, the flow controller readjusted its output to
cancel the effect of the feedforward signal and maintain flow at its setpoint. To work as expected, the feedforward action
would have to be on the flow controller setpoint - multiplied by a not summed with the pH controller output. Multiplication will
force the reagent flow to zero if the process fluid flow is zero or the fluid is at the setpoint. Also for you control jocks,
multiplication cancels composition loop gain - a term inversely proportional to sump flow. This leads to Fact of Life #6.

All of these corrections are reflected in Figure 2b above. The system, as shown, has been controlling well since startup.

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Where's the agitator?

A process used a vertical tank of neutralization. Performance was poor because response was slow and the effluent was not
uniformly mixed. I looked at the drawings and noted that the vertical unit seemed a bit tall for its diameter. I asked how high
it was, and the designer said, "50 feet," I gasped, "It's not nice to kid an old engineer." He responded, "Who's kidding?" He
replied, "You're the only agitator on this project." I instantly knew I had a major problem.

FIGURE 3. Where's the agitator? (a)-unsuccessful and (b)-successful pH control systems for a process involving an extremely
tall mixing tank without an agitator

. Figure 3a shows how the pH was originally being controlled. Axial agitation probably would have corrected the difficulties, but
could not be provided economically because the tank was too tall. A shorter tank would also have worked - again at a higher
price than the plant wanted to pay. I decided that the best way to cope with the tank would be to use its volume as a filter,
estimating that it would attenuate the hydrogen ion concentration oscillations of an in-line loop by a factor of 10,000 - 4 pH
units. A circulation pump was installed as a low-deadtime in-line mixer. Influent and reagent were added to the new suction;
an injector probe was installed on the pump discharge. The new system is shown in Figure 3b.

Upsets still occurred, due mainly to the quick opening characteristic and the large positioner hysteresis of the plug valve on
the influent. However, the in-line pH loop returned rapidly to setpoint after a disturbance. Further, after passing through the
tank volume, the pH drew the straightest line I have ever seen; for a moment, we thought someone had tied down the
pointer. Performance was so good that the plant suggested we standardize on this type of system for pH control. I warned
them that the setpoint of this system was several pH units below the neutral zone, on a relatively flat position of the titration
curve. On a steep part of the curve, Fact of Life #2 would prevail and there would be lots of oscillations.

FIGURE 4. Where's the electrode? (a)-unsuccessful and (b)-successful pH control systems for a process in which electrodes
have to be installed in inconvenient locations.

Where's the electrode?

I was called in to troubleshoot the pH system shown in Figure 4a. This simple configuration should have worked flawlessly, but
was plagued by an unacceptably wide control band about the setpoint. I went down to look at the exit nozzle of the vessel and
couldn't find the electrodes. I rapidly surmised that I had a major problem. In this case, the source of the difficulty was
political. The instrument maintenance department had specified that the electrodes be located in the analyzer house, to avoid
the discomfort of servicing them outside during the winter. Unfortunately, this location introduced excessive deadtime in the
loop. To help avoid this problem in other situations, I feel compelled to state Fact of Life #7.

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I succeeded in getting the electrodes moved by arguing about the extreme safety hazards and product quality problems that
accompanied large pH excursions. The change, indicated in Figure 4b, narrowed the control band to about 0.1 pH.

We used injector electrodes for this application. Experience shows that these provide better performance and require less
maintenance than sample chamber electrode holders. These benefits are especially evident when the electrodes are mounted
in the discharge nozzle piping where fluid velocity is high - because the flow ensures rapid response by minimizing boundary
layer thickness and prevents electrode coating by impurities in the stream.

Injection electrodes also appear to be less prone than sample chamber elements to leakage. In checking 30 installations of
injection devices from one manufacturer, I found no instances of leakage; in fairness, when we obtained products from a
different source, some leakage did occur. However, every sample chamber electrode holder I have ever encountered has
eventually leaked. Moreover, leakage is visible with injector assemblies but not with sample chambers. For hazardous fluids,
you don't want any surprises when you open the top cover of the electrode holder. This leads me to Fact of Life #8.

Is bigger better?

A plant used the system of Figure 5a for waste neutralization. The eductor shown in the figure had been added because mixing
deadtime was too long. But even with this device, the deadtime appeared to be over 40 minutes. The consequent natural
period of the pH loop was 160 minutes, so the maximum reset should have been less than 0.01 repeats per minute. Since this
was below the minimum setting on the controller, the loop was in a continuous reset cycle; further, the integrated error -
which is proportional to the deadtime squared - was out of this world. I looked at the engineering flow diagram and spotted
the largest storage tank I had ever seen. I asked the process engineer where the neutralization tank was, and he pointed to
the elephant I just thought was for storage. I immediately understood that I had major problem.

The intent of the large tank was plausible. It would serve to blend acidic and basic waste streams from different sources and
minimize the reagent demand. Now, as long as you don't have to put control loops on them, large tanks are useful. Upstream
of a control loop, a large tank can filter out disturbances and reduce reagent requirements; downstream, it can filter out loop
oscillations - which is particularly advantageous because these fluctuations are usually faster than variations in influent
concentration and are therefore more effectively attenuated. This reminds me of Fact of Life #9.

FIGURE 5. Is bigger better? (a)-unsuccessful and (b)-successful pH control systems for a process in which an extremely large
tank was initially employed for mixing.

The new control system is shown in Figure 5b. The large tank was replace with two small vessels in series. A pulse frequency
controller was installed to avoid valve pluggage at low reagent flows and to meet the extreme rangeability requirements
imposed by the wide variations in influent flow and pH. Signal characterization was used to counteract the steep slope of the
titration curve at the setpoint.

Startups are no fun without magical mystery. In this instance, we noticed that the pH measurement on the first tank was
erratic. The problem could not be duplicated when we removed the electrodes and inserted them directly into the buffer
solution or connected them to the measurement system of the second tank. We replaced the pH transmitter, preamplifier,
cable, and electrodes individually but the erratic measurements continued. Eventually, someone remembered that the
fiberglass preamplifier enclosure supplied by the manufacturer was replaced by the field maintenance department with a metal
housing - to provide more room for access. The enclosure mounting plate was grounded. This created a second ground point
in the circuit, and caused a significant current flow through the circuit. The problem did not occur on the second tank because
the preamplifier housing was not mounted on a conductive structure. Likewise, the erratic behavior was not observed during
buffering because the bottle was plastic. The problem was solved by isolating the preamplifier enclosure from ground with a
plastic mounting plate.

The control system has performed well from startup except for periodic pluggage of the electrodes in an overflow sample line.
Liquid head is too low to achieve a sample velocity sufficient to sweep the electrodes clean. A new electrode holder that
provides a large flat electrode surface will be tried. If that doesn't work, we may have to shake loose enough money to install
a sample pump and an injector electrode assembly.
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Where's the reagent piping?

The pH in a neutralization tank was fluctuating in what appeared to be a square wave. The system was also subject to periodic
glass electrode failures caused by etching and severe upsets due to a high-temperature interlock that sets due to a high-
temperature interlock that shut off the reagent flow. Plant people were especially anxious to improve this system because
reliability was critical to plant productivity. I stood at the top of the vessel wondering what to do, and noticed that the reagent
was being transported by a conveyor rather than a pipe. I soon perceived that I had a major problem.

FIGURE 6. Where's the reagent piping? (a)-unsuccessful and (b)-successful pH control systems for a process iin which a
powdered line reagent is delivered by a conveyor.

Figure 6a shows the original installation. The reagent, pulverized lime, was controlled by a rotary feeder at the discharge of
the hopper. Feeder speed was set by the pH controller output. Reagent delivery was subject to several minute's lag due to
transportation delay on the conveyor and solids dissolution time. We made precise measurements of the pH in the tank and
found that the square waves were worse than the plant thought - the process instruments recorded only the high end of the
pH scale, but the fluctuations actually covered almost the whole range from 0 to 14.

Luckily, a huge tank upstream of the waste flow provided enough inventory so the pH controller could be used to throttle the
waste stream. The lime feeder speed was determined by selecting the lower of a manually-entered throughput setpoint and a
command from the temperature override controller. The low signal selector therefore provided smooth transition between
between normal and override control. The feeder speed signal is also multiplied by the pH controller command, passed
through a lag unit whose delay is set equal to the reagent delivery time, and fed forward to establish the waste flow setpoint.

To eliminate downtime due to electrode failures, a system was installed using three measuring elements and voting logic to
establish the output signal. Use of three rather than two electrode assemblies make it possible to determine which signal to
use, if the electrode outputs disagree. This leads me to Fact of Life #10.

Control improved dramatically. Electrode failure due to etching, which had occurred when the solution was acidic - at the
unrecorded lower portion of the square wave - also stopped. And use of voting logic to control using three electrode
assemblies has virtually eliminated downtime, even when an element becomes nonfunctional.

USING YOUR SKILLS

One of the prices you pay for being an instrumentation expert in the processing industries is that occasionally, someone will
ask you to control pH. The job rarely proves to be easy, for instance because you are on a flat portion of the titration curve or
have wide tolerance on response and accuracy, because changes are then high that someone has done it satisfactorily without
you. So the problems you get are usually major problems. You'll have to call on all you know about the installation and
operation of electrodes, control valves, piping, and mixing equipment. You'll have to brush the cobwebs off your basic
understanding of feedback and feedforward loop strategies. You'll have to home your skills as a diplomat to get the plant to
install, replace, or eliminate vessels or instruments that make life convenient for the operators or maintenance people - or
represent investments for which somebody has a neck on the line - but are preventing satisfactory pH control. And you'll have
to resign yourself to living out of your suitcase for a while while the plant starts up and experiences the magical mystery of
pH.

REFERENCE

1. McMillian. G K; pH Control. Independent Learning Module Series, Instrument Society of America (Research Triangle Park
NC), 1964.

© Instruments Society of America. Intech, September, 1984. All rights reserved.

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