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The Science of pH in Skincare

Why pH determines whether your glycolic acid product actually works. Learn about pKa, free acid value, the Henderson-Hasselbalch equation, and optimal pH ranges.

Updated Feb 22, 2026
16 min read

Educational content only. This article is not personal medical advice. For guidance specific to your skin, medications, or conditions, consult a board-certified dermatologist.

The percentage on the label of your glycolic acid product is only half the story. A 10% glycolic acid serum at pH 3.0 delivers roughly three times more active acid to your skin than a 10% glycolic acid product at pH 4.5. The difference is pH - and understanding it transforms you from a passive consumer into someone who can evaluate whether a product will actually work. This article explains the chemistry behind pH in skincare, why it matters so much for acid efficacy, and how to use this knowledge when choosing products [1].

Glycolic Acid pKa

3.83

At this pH, exactly 50% of glycolic acid molecules are in their active (protonated) form. Below this pH, more acid is active; above it, less.

Skin's Natural pH

4.5 – 5.5

The acid mantle - your skin's protective layer - maintains a mildly acidic environment that supports barrier function and microbiome health.

CIR Safety Minimum

pH 3.5

The Cosmetic Ingredient Review Expert Panel considers pH 3.5 the minimum safe level for consumer glycolic acid products at concentrations up to 10%.

What Is pH?

pH is a measure of how acidic or alkaline a solution is. The scale runs from 0 (extremely acidic) to 14 (extremely alkaline), with 7 being neutral - pure water.

The scale is logarithmic, which means each whole number change represents a tenfold difference in acidity. A solution at pH 3.0 is ten times more acidic than one at pH 4.0, and one hundred times more acidic than one at pH 5.0. This is why seemingly small differences in pH - like the difference between pH 3.5 and pH 4.0 - can have significant effects on how a skincare product performs.

For glycolic acid products, pH determines how much of the acid exists in its active form. This is not a marketing concept - it is a consequence of fundamental acid-base chemistry that governs every acid product you use.

The pKa of Glycolic Acid

Every acid has a characteristic property called its pKa - the pH at which exactly half of its molecules are in the protonated (active) form and half are in the deprotonated (inactive) form. The pKa of glycolic acid is 3.83, and this single number governs everything about how glycolic acid products behave [2].

Here is what this means practically:

  • Below pH 3.83: More than half the glycolic acid molecules are protonated - in their active form, capable of penetrating the skin and exfoliating.
  • At pH 3.83: Exactly 50% of the glycolic acid is active.
  • Above pH 3.83: Less than half the glycolic acid is active. The higher the pH goes, the more the acid converts to its ionized, inactive form.

Think of it this way: the pKa is the tipping point. Below it, the acid is predominantly "armed." Above it, the acid is predominantly "disarmed." And the further you move from the tipping point in either direction, the more extreme the ratio becomes.

Why pKa Matters for Different AHAs

Different alpha-hydroxy acids have different pKa values, which affects how they must be formulated:

| AHA | pKa | Implication | |-----|-----|-------------| | Glycolic acid | 3.83 | Most active at pH below 3.83 | | Lactic acid | 3.86 | Very similar to glycolic acid | | Mandelic acid | 3.41 | Needs lower pH for equivalent activation | | Citric acid | 3.13 (first) | First proton releases at lower pH |

Glycolic acid's pKa of 3.83 means it can deliver meaningful free acid at pH levels that most skin can tolerate (3.5–4.0). This is one of the reasons glycolic acid remains the most widely used AHA in both clinical and consumer settings.

The Henderson-Hasselbalch Equation

The relationship between pH and the active fraction of an acid is described by the Henderson-Hasselbalch equation:

pH = pKa + log([A-] / [HA])

Where:

  • pH = the pH of the solution
  • pKa = the acid dissociation constant (3.83 for glycolic acid)
  • [A-] = concentration of the deprotonated (inactive, ionized) form
  • [HA] = concentration of the protonated (active, un-ionized) form

Rearranging this equation lets us calculate the percentage of glycolic acid in its active form at any given pH. This is what skincare chemists call the free acid value - the percentage of the listed glycolic acid concentration that is actually doing work on your skin.

Free Acid Value: Where pH Meets Concentration

The free acid value (FAV) is the actual amount of active glycolic acid in a product. It combines two pieces of information: the listed concentration and the product's pH.

Free Acid Value = Listed Concentration x Fraction in Protonated Form

The fraction in the protonated form comes directly from the Henderson-Hasselbalch equation. For a detailed explanation of free acid value and why it matters more than what is on the label, see our dedicated article on free acid value explained.

Example: 10% Glycolic Acid at Different pH Values

Let us work through what happens to a 10% glycolic acid product at four different pH values. These calculations show why pH is not just important - it is decisive.

| pH | % Active (Protonated) | Free Acid from 10% Product | Relative Potency | |----|----------------------|---------------------------|-------------------| | 3.0 | 87.1% | 8.7% | Highest | | 3.5 | 68.1% | 6.8% | High | | 3.83 (pKa) | 50.0% | 5.0% | Moderate | | 4.0 | 40.3% | 4.0% | Moderate-Low | | 4.5 | 17.6% | 1.8% | Low | | 5.0 | 6.3% | 0.6% | Minimal |

The difference is striking. Moving from pH 3.0 to pH 4.5, the active acid drops from 8.7% to 1.8% - a nearly fivefold reduction - from the same "10% glycolic acid" product. This is why pH is not optional information; it fundamentally determines what the product does [3].

Why Two "10% Glycolic Acid" Products Can Be Completely Different

This is perhaps the most practically important implication of pH science. Consider two hypothetical products:

Product A: 10% glycolic acid, pH 3.2

  • Free acid value: approximately 8.1%
  • Delivers strong exfoliation. Noticeable tingling. Visible results quickly. Higher irritation risk.

Product B: 10% glycolic acid, pH 4.5

  • Free acid value: approximately 1.8%
  • Delivers mild exfoliation. Little to no tingling. Slower results. Very well tolerated.

Both labels say "10% glycolic acid." Both are telling the truth. But Product A delivers more than four times the active acid of Product B. A consumer who switches from Product A to Product B expecting the same results will be disappointed. A consumer who switches from Product B to Product A without adjusting their routine risks significant irritation.

This is not a theoretical problem. It happens constantly because most brands do not disclose the pH of their products - and even those that do rarely explain what it means. Our concentration guide helps navigate this, but the bottom line is simple: percentage without pH is incomplete information.

The Skin's Natural pH: The Acid Mantle

Your skin is not pH-neutral. The surface of healthy skin maintains a pH of approximately 4.5 to 5.5, creating what dermatologists call the acid mantle - a thin, slightly acidic film formed by sebum, sweat, and dead cell breakdown products [4].

The acid mantle serves several protective functions:

  • Barrier integrity: The enzymes responsible for processing ceramides and other lipids that form the skin barrier work optimally at acidic pH. Disrupting this pH impairs barrier function.
  • Microbiome regulation: The skin's resident beneficial bacteria (the microbiome) thrive in the 4.5–5.5 range. Pathogenic bacteria generally prefer neutral to alkaline conditions.
  • Antimicrobial defense: The acidic environment itself inhibits the growth of harmful microorganisms.
  • Enzyme regulation: Many skin enzymes, including proteases involved in desquamation (natural shedding), are pH-dependent.

How Acid Products Interact with the Acid Mantle

When you apply a glycolic acid product at pH 3.0–4.0 to skin at pH 4.5–5.5, several things happen:

  1. Local pH drops temporarily at the application site, activating the glycolic acid.
  2. Skin buffers resist the pH change. Your skin is not a passive surface - it actively resists pH changes through buffering capacity in the stratum corneum.
  3. Over minutes to hours, skin pH returns to its natural range as the product is absorbed, diluted by sweat, and buffered by the skin.
  4. The acid does its work during the window of lowered pH - exfoliating by disrupting desmosomes (the protein "rivets" holding dead skin cells together) and stimulating cellular turnover [5].

This interaction is why healthy skin with an intact acid mantle tolerates properly formulated acid products. The skin's buffering capacity is a natural safeguard. However, when the acid mantle is already compromised - from over-exfoliation, harsh cleansers, or conditions like eczema - the skin cannot buffer effectively, which is when irritation becomes more likely.

Buffered vs. Unbuffered Formulations

Not all glycolic acid products start at the same pH, even at the same concentration. This is because formulation chemists can choose to make products buffered or unbuffered - and this choice significantly affects the product's behavior on the skin.

Unbuffered (Free Acid) Formulations

An unbuffered glycolic acid product contains the acid in its natural state without added neutralizing agents. The pH is determined solely by the concentration of glycolic acid and the solvent. These products tend to have lower pH values and higher percentages of free acid, making them more potent - and more irritating.

Unbuffered formulations are common in professional peels and some high-performance consumer products. They deliver more active acid per application but require more caution and tolerance.

Partially Neutralized (Buffered) Formulations

A buffered glycolic acid product has had some of its acid neutralized by adding a base (commonly ammonium hydroxide, sodium hydroxide, or arginine). This raises the pH without removing glycolic acid from the formula - but it converts some of the active (protonated) glycolic acid into its inactive (ionized) salt form.

The result is a product that still lists the same glycolic acid percentage on the label but delivers less free acid. The trade-off is intentional: reduced potency in exchange for improved tolerability.

Which Is Better?

Neither is inherently superior. The right choice depends on your skin's tolerance, your goals, and where you are in your glycolic acid journey:

  • First-time users: Buffered formulations at pH 3.8–4.2 provide a gentler introduction with lower risk of irritation.
  • Experienced users seeking stronger results: Lower-pH, less-buffered formulations deliver more active acid. Approach gradually.
  • Sensitive skin: Higher-pH buffered formulations or lower concentrations may be the only viable option.
  • Professional peels: These are typically unbuffered at low pH (2.0–3.0) for maximum penetration, which is why they require professional supervision.

The study by Narda et al. (2021) demonstrated that glycolic acid adjusted to pH 4 stimulated collagen production and epidermal renewal without increasing pro-inflammatory TNF-alpha - showing that partially neutralized formulations retain meaningful skin benefits without triggering inflammation [6].

Optimal pH Ranges for Glycolic Acid Products

Based on the clinical evidence and regulatory guidelines, here is how different pH ranges affect glycolic acid performance:

pH 2.0–3.0: Professional Peel Territory

At this pH range, 87–99% of glycolic acid is in its active form. This delivers maximum exfoliation and penetration but carries significant irritation risk. Products in this range should only be used under professional supervision with controlled contact times. The Kaminaka et al. (2014) RCT used 40% glycolic acid at pH 2.0 for acne treatment - effective, but a professional setting [7].

pH 3.0–3.5: High Potency Consumer Products

Approximately 68–87% of glycolic acid is active. This is the range where well-formulated consumer products deliver noticeable results. The Cosmetic Ingredient Review Expert Panel considers pH 3.5 the minimum for consumer products at up to 10%(Low concentration) concentration [8]. Products at the lower end of this range (pH 3.0–3.2) are potent and may not suit beginners.

pH 3.5–4.0: The Balanced Zone

Roughly 40–68% of glycolic acid is active. This range represents a practical balance between efficacy and tolerability for most users. Many well-regarded consumer glycolic acid products are formulated in this zone. Kaidbey et al. (2003) tested 10%(Low concentration) glycolic acid at pH 3.5 and found measurable UV sensitization - confirming biological activity at this pH [9].

pH 4.0–4.5: Gentle / Sensitive Skin Range

Only 18–40% of glycolic acid is active. Products in this range are considerably gentler. They are appropriate for sensitive skin or as an introductory step. The Abels et al. (2011) RCT demonstrated that even 10%(Low concentration) glycolic acid at pH 4.0 significantly improved mild acne versus placebo - evidence that glycolic acid remains effective even at higher pH values, though with less intensity [10].

pH Above 4.5: Minimal Activity

Less than 18% of glycolic acid is active. At pH 5.0, only about 6% remains protonated. Products at this pH are very mild but deliver limited exfoliation. Some brands formulate at higher pH to make products gentler, but this substantially reduces what the glycolic acid actually does. At pH 6.0, less than 1% of the acid is active - essentially inactive as an exfoliant.

US vs. EU Regulatory Standards

The regulatory approach to glycolic acid pH differs significantly between the United States and the European Union, and this affects what products are available in each market:

| Parameter | US (CIR/FDA) | EU (SCCS) | |-----------|-------------|-----------| | Maximum consumer concentration | 10% | 4% | | Minimum pH | 3.5 | 3.8 | | Professional use threshold | Not explicitly defined | Above 4% or below pH 3.5 |

These differences mean that a product considered standard in the US (for example, 10% glycolic acid at pH 3.5) would be restricted to professional use in the European Union. EU consumers have access to gentler products but fewer high-potency options without visiting a professional [8].

Common Misconceptions About pH in Skincare

"Lower pH is always better"

Not true. Lower pH means more active acid, but more active acid is not always desirable. The goal is not maximum acid activity - it is the right amount of activity for your skin. Over-exfoliation from products with too-low pH can damage the skin barrier, cause chronic irritation, and paradoxically worsen the skin problems you are trying to solve.

"pH-balanced means pH 7"

A common misunderstanding. When skincare products claim to be "pH-balanced," they typically mean balanced with the skin's natural pH (4.5–5.5), not neutral pH 7. A pH 7 cleanser would actually be too alkaline for optimal skin health.

"You can test product pH with pH strips and get an exact reading"

Consumer-grade pH strips give approximate readings, not precise ones. They are useful for rough categorization (is this product in the 3–4 range or the 4–5 range?) but should not be relied upon for exact free acid calculations. Professional-grade pH meters are far more accurate but expensive and require calibration.

"The pH of my product changes after I apply it"

This is actually true, but it is not a concern. When the product meets your skin's buffering system, the pH at the skin surface shifts toward the skin's natural range over time. This is normal and expected. The product does its work during the initial contact period when pH is lowest, and the skin gradually returns to its baseline.

"Mixing vitamin C and glycolic acid is dangerous because of pH"

Both vitamin C (L-ascorbic acid) and glycolic acid function at low pH, so using them together does not create a dangerous pH situation. The concern with combining them is over-irritation from using two potent actives simultaneously, not a chemical reaction. If your skin tolerates both, the pH profiles are actually compatible. However, layering many actives increases total irritation potential, regardless of pH compatibility [11].

Practical Takeaways

  1. Always look for pH information. If a brand does not disclose it, you can contact them or test it yourself with pH strips for an approximation. A glycolic acid product without pH information is like a medication without dosage information. Our product database includes pH data where available to help you evaluate products.

  2. Use the free acid calculator to understand what you are actually applying. Enter the concentration and pH, and make informed decisions rather than relying on the label percentage alone.

  3. Match pH to your experience level. If you are new to glycolic acid, start with products at pH 3.8–4.2. As your skin builds tolerance, you can move to lower-pH products if desired. See our how to use glycolic acid guide for a step-by-step protocol.

  4. Do not chase the lowest pH. More active acid is not always better. The optimal pH for you is the one that delivers results without exceeding your skin's tolerance threshold.

  5. Sunscreen is mandatory at any effective pH. Research demonstrates that glycolic acid at clinically active pH levels increases UV sensitivity [9]. Broad-spectrum SPF 30 or higher is non-negotiable, as detailed in our side effects and safety guide.

  6. Understand that concentration and pH work together. A 5%(Low concentration) glycolic acid product at pH 3.0 delivers more free acid (4.4%) than a 10%(Low concentration) product at pH 4.5 (1.8%). The percentage on the label is important, but it is incomplete without pH context - and the science confirms this [3].

References

  1. 1. Sharad J. (2013). Glycolic acid peel therapy - a current review. Clin Cosmet Investig Dermatol. doi:10.2147/CCID.S34029Review
  2. 2. Green BA, Yu RJ, Van Scott EJ. (2009). Clinical and cosmeceutical uses of hydroxyacids. Clin Dermatol. doi:10.1016/j.clindermatol.2009.06.023Review
  3. 3. Decker LC, Graber EM. (1996). Clinical and histological effects of glycolic acid at different concentrations and pH levels. Dermatol Surg. doi:10.1111/j.1524-4725.1996.tb00341.xClinical study
  4. 4. Lambers H, Piessens S, Bloem A, Pronk H, Finkel P. (2006). Natural skin surface pH is on average below 5, which is beneficial for its resident flora. Int J Cosmet Sci. doi:10.1111/j.1467-2494.2006.00344.xClinical study
  5. 5. Fartasch M, Teal J, Menon GK. (1997). Mode of action of glycolic acid on human stratum corneum: ultrastructural and functional evaluation of the epidermal barrier. Arch Dermatol Res. doi:10.1007/s004030050212Mechanistic study
  6. 6. Narda M, Trullas C, Brown A, et al. (2021). Glycolic acid adjusted to pH 4 stimulates collagen production and epidermal renewal without affecting levels of proinflammatory TNF-alpha in human skin explants. J Cosmet Dermatol. doi:10.1111/jocd.13570Ex vivo study
  7. 7. Kaminaka C, Uede M, Matsunaka H, Furukawa F, Yamamoto Y. (2014). Clinical evaluation of glycolic acid chemical peeling in patients with acne vulgaris: a randomized, double-blind, placebo-controlled, split-face comparative study. Dermatol Surg. doi:10.1111/dsu.12417RCT
  8. 8. Andersen FA. (1998). Final Report on the Safety Assessment of Glycolic Acid, Ammonium, Calcium, Potassium, and Sodium Glycolates.... Int J Toxicol. doi:10.1177/109158189801700101Safety assessment
  9. 9. Kaidbey K, Sutherland B, Bennett P, et al. (2003). Topical glycolic acid enhances photodamage by ultraviolet light. Photodermatol Photoimmunol Photomed. doi:10.1034/j.1600-0781.2003.00013.xRCT
  10. 10. Abels C, Kaszuba A, Michalak I, et al. (2011). A 10% glycolic acid containing oil-in-water emulsion improves mild acne: a randomized double-blind placebo-controlled trial. J Cosmet Dermatol. doi:10.1111/j.1473-2165.2011.00572.xRCT
  11. 11. Tang SC, Yang JH. (2018). Dual Effects of Alpha-Hydroxy Acids on the Skin. Molecules. doi:10.3390/molecules23040863Review

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