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S P E C I A L F E A T U R E

What Is the Critical pH and
Why Does a Tooth Dissolve in Acid?
• Colin Dawes, BSc, BDS, PhD •

A b s t r a c t
This paper discusses the concept of critical pH for dissolution of enamel in oral fluids. The critical pH does not have
a fixed value but rather is inversely proportional to the calcium and phosphate concentrations in the solution. The
paper also discusses why teeth dissolve in acid, why remineralization of white-spot caries lesions is possible and
why remineralization of teeth eroded by acid is not possible.

MeSH Key Words: dental enamel solubility; hydrogen-ion concentration; tooth remineralization

© J Can Dent Assoc 2003; 69(11):722–4
This article has been peer reviewed.

A
recent article in this journal1 referred frequently to and varies slightly from person to person. Nevertheless, the
the critical pH of dental enamel as 5.5, as though factors that influence the solubility of enamel’s primary
this were a fixed value, independent of the component, HA, also influence the solubility of enamel.
composition of the solution to which enamel is exposed. In When HA is in contact with water, the following reac-
fact, the critical pH varies over a wide range, its value tion occurs:
depending on the concentrations of calcium and phosphate ➞
Precipitation ➞ Dissolution
in the solution. ➞
Ca10(PO4)6(OH)2 ➞ 10Ca2+ + 6PO43– + 2OH–
The critical pH is the pH at which a solution is just ➞
Solid ➞ Solution
saturated with respect to a particular mineral, such as tooth
enamel. If the pH of the solution is above the critical pH, A small amount of HA dissolves, releasing calcium,
then the solution is supersaturated with respect to the phosphate and hydroxyl ions. This process continues until
mineral, and more mineral will tend to precipitate out. the water is saturated with respect to HA. At that point, the
Conversely, if the pH of the solution is less than the critical rate of the forward reaction (mineral dissolution) is equal to
pH, the solution is unsaturated, and the mineral will tend the rate of the backward reaction (mineral precipitation).
to dissolve until the solution becomes saturated. The solubility of a substance such as HA, which can split
The concept of critical pH is applicable only to solutions into separate ions, is characterized by its solubility product,
that are in contact with a particular mineral, such as or Ksp, the product of the concentrations (mol/L) of the
enamel. Saliva and plaque fluid, for instance, are normally component ions, raised to the appropriate power, in a satu-
supersaturated with respect to tooth enamel because the rated solution. Thus, for a solution saturated with respect
pH is higher than the critical pH, so our teeth do not to HA, the Ksp is [Ca]10[PO4]6[OH]2. Strictly speaking,
dissolve in our saliva or under plaque. However, these fluids the values within brackets represent the activities (effective
cannot be supersaturated with respect to individual ions, concentrations) of the component ions rather than their
such as calcium or phosphate, as some authors state.1 actual concentrations. The activities are inversely propor-
Dental enamel is composed primarily of hydroxyapatite tional to the concentrations of other ions, such as sodium
(HA), Ca10(PO4)6(OH)2, but it also contains several and potassium, that are present. Because HA is a highly
impurities such as carbonate and fluoride. Because the insoluble mineral, and because the activities of the 3 compo-
proportions of these impurities vary from person to person, nent ions are expressed in the large units of moles per litre,
and indeed from tooth to tooth, and because the impurities the measured value of Ksp for HA is very small, on the
can influence enamel solubility, that solubility is not fixed order of 10–117. Although the Ksp is a constant, the

722 December 2003, Vol. 69, No. 11 Journal of the Canadian Dental Association

The most in acid. concentrations. the total phosphate concentration is 5 × 10–3 mol/L. the water is concentration of 5 × 10–3 mol/L. saliva or plaque fluid is present in 4 different forms. the lower the concen- phosphate and hydroxyl ions. is applied for only about 10 s. because the levels and thus the Ip for HA is zero. Figure 1 illustrates how the to which they are susceptible. 11 723 . whereas in those with high salivary calcium and phosphate often to a value less than the Ksp. and which has a pH of about 1 (Fig. and the proportions exposure to fluoride rinses or gels to reduce the risk of caries depend entirely on the pH. potential to cause erosion because many of them have a pH Second. which usually employs as low as 5. a tooth will dissolve in saliva Ip of HA. the critical pH is not a constant. it contains no Figure 1: The effect of pH on the concentrations of the various inorganic phosphate species in saliva containing a total phosphate calcium or phosphate ions. it may be 5. PO43. the only species that contributes to the Ip > Ksp for HA. the solu. n For any given solution. and if o L -13 Ip > Ksp. 1). Therefore. proportions of the 4 phosphate species vary with pH when such as a sodium fluoride solution. This solution contains no calcium Thus.5. The more calcium and phosphate that are present the enamel is limited. a tooth will dissolve to some extent in any solu- tion in which calcium and phosphate ions are not present. in which t gastric soft Saliva pH range juice drinks the hydroxyl concentration is reduced. 37% phosphoric acid. 1). the ion product (Ip) is deter. which usually contain 0. a 0 2 4 6 8 10 12 14 small amount will slowly dissolve (about 30 mg in 1 L of pH water). as any solution is acidified. or plaque fluid only if the pH is reduced to less than the Thus. Because Ip < Ksp. provided that their product remains i pH of pH of most equal to the Ksp.1 mol/L phosphoric acid in addition to the sodium fluoride and Why Does a Tooth Dissolve in Acid? which have a pH of 2. H2PO4–.3 The fluid phase of dental Clinically. the solution is unsaturated. as follows: H+ + OH– ➞ H2O. Again. there are 2 situations in which dentists place plaque contains much higher concentrations of calcium acid in contact with enamel and in which enamel dissolves. e -5 c gastric juice or a soft drink.2 The Ip for HA in distilled water is zero. is virtually independent of pH. Thus. The lower the pH. Likewise. Hence. First. In people with low salivary concentrations tration is unaffected but the concentrations of both of calcium and phosphate. The product ric acid and low concentrations of calcium and phosphate of [H+][OH–] in water always equals 10–14 (mol/L)2. Other sources of Therefore. typical of saliva. H2PO4- Ip = Ksp. The second situation is the use of in a solution. the solubility of HA in water is about sure time of 4 min with these gels. and phosphate than does saliva. the acid of calcium and phosphate in plaque fluid vary among indi. the critical pH may be 6. such as essentially no calcium and the Ip for HA is zero. the hydrogen ions remove hydroxyl ions ➞ devastating acid is gastric juice. the inorganic phosphate in any fluid such as of less than 3 (Fig. phosphate and hydroxyl concentrations. which have great [OH–] must decrease in a reciprocal manner. H 3PO4 -15 When a tooth is placed in distilled water of pH 7.2 Patients. plaque fluid.1. it is important not to exceed an expo- in pH. To avoid excessive enamel Journal of the Canadian Dental Association December 2003. acid fluorophosphate gels. because although the water contains hydroxyl ions. whereas at pH 4 it is about 30 g/L. then the solution is just saturated with respect g -11 to HA. though. If HPO42. namely Patients with severe xerostomia usually require daily H3PO4. 30 mg/L. At pH 7. the acid include fruit juices and soft drinks. If Ip < Ksp. is the Ip. Vol. in a more acidic solution. and most of the time tration of PO43–. the concentrations a -1 Log concentration (mol/L) Plaque fluid pH range r of the calcium or phosphate ions (or both) would have to t -3 increase if saturation were to be maintained. Normally. What Is the Critical pH and Why Does a Tooth Dissolve in Acid? concentrations of each of the 3 component ions in a satu- o rated solution can vary.5. which sodium chloride. to avoid bility of HA increases about 10-fold for each unit decrease excessive enamel loss. No. saliva and plaque fluid do contain calcium.3.4 and its critical pH may be The first is the acid-etch technique. of course. may also introduce acid into their There are 2 reasons for the increased solubility of enamel mouths. OH– and PO43– are reduced and so. as is In contrast. these gels contain Although the solubility of some minerals. concentration of PO43– (thick line) as the pH is reduced. the calcium concen- critical pH. where it can cause erosion of enamel. means that the tooth will begin to dissolve. There is a marked fall in the unsaturated and the tooth will dissolve until Ip = Ksp. so potential dissolution of viduals.1 which contains hydrochlo- to form water. therefore. HPO42– and PO43–. such as saliva. n -7 mined by means of a similar calculation. 69. the solution is supersaturated. as the [H+] increases in an acid solution. the lower its critical pH. also based on o c -9 the calcium.

E-mail: Colin_Dawes@umanitoba. University of Manitoba. contrary to some views. Inorganic constituents of saliva in relation to caries. particularly when salivary flow is stimulated. but teeth that have suffered acid erosion cannot. Teeth with early subsurface caries lesions can be remineralized. Investigations into the calcium Can Decalcified Enamel Be Remineralized? phosphate equilibrium between enamel and saliva and its relation to dental caries. the decalcification has 4. No. Ericsson Y.ca.6 and because the subsurface lesion provides a suitable matrix for crystal growth after calcium and phosphate ions have passed through the pellicle and surface enamel. 3. Winnipeg. Faculty of Dentistry. Dawes C. which is why it is so important for dentists to check for its occurrence and thus allow patients to take appropriate measures to reduce further exposure of their teeth to acid. Acta Odont Scand 1949. In addi- tion. salivary flow is gums. has the effect of reducing the critical pH. p. Copenhagen: Munksgaard. Sàndor GK.5 Such remineral- ization can take place only because saliva and plaque fluid are normally supersaturated with respect to tooth mineral. adequate or is regularly stimulated by use of sugar-free gum..Dawes decalcification in such patients. provided they are kept free of plaque. the presence of the enamel pellicle prevents the teeth from enlarging continuously.5 because there is no suitable matrix for crystal growth. Colin Dawes. Dawes C. Department of Oral Biology. J Can Dent Assoc 2003. Larsen MJ. An enamel surface eroded by acid becomes covered by an acquired enamel pellicle of salivary and bacterial proteins as soon as it contacts the saliva. The author has no declared financial interests. Vol. Bruun C. occurred below the surface. ten Cate JM. a neutral sodium fluoride References gel or rinse rather than an acidulated fluorophosphate 1. 11 Journal of the Canadian Dental Association . 8(Suppl 3):1–139. Manitoba. In a white-spot caries lesion. Correspondence to: Dr. C Dr. 69(2):84–9. Enamel/saliva – inorganic chemical reactions. editor. 69. 40(8):699–705. being less soluble than hydroxy. Barron RP. If saliva contacts enamel after acid etching. There is very good clinical evidence that vitro. and this pellicle inhibits mineral deposition. Thus. 1984. p. Remineralization of artificial enamel lesions in about 0. Dawes is professor of oral biology. and the lesion is covered by a In: Guggenheim B. faculty of dentistry. 1986. Fejerskov O. University of Manitoba. Dental erosion in gastroesophageal reflux disease. and topical fluoride treatments are given. Arch Oral Biol 1995. 11(5):277–86. Cariology today.03 mm. In: Thylstrup A. the critical pH below which enamel dissolves is not constant but rather is inversely proportional to the concentrations of calcium and phosphate in the saliva and plaque fluid. Enamel-apatite solubility. Arends J. such lesions can be remineralized if the surface remains 6. 780 Bannatyne Ave.1 enamel erosion is irreversible. the pellicle that forms also reduces the strength of bonding to composite resin. Conclusions In summary. virtually intact surface zone of enamel with a thickness of 5. apatite. to form fluorapatite which. The flow rate and electrolyte composition of whole saliva elicited by the use of sucrose-containing and sugar-free chewing- intact. Winnipeg MB R3E 0W2. 724 December 2003. Marcon MA. Carmichael RP. enamel that has suffered surface erosion by acid cannot be recalcified. Textbook of cariology. The fluoride reacts with enamel 2. In contrast. even though they are bathed in saliva supersaturated with tooth mineral. Basel: Karger. editors. 70–4. gel should be employed. Dong C. 181–203. Caries Res 1977.