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Yeast Fermentation Yeast fermentation is used in many standardized products such as bread and rolls. By far, the majority of baked products manufactured in the world rely on yeast fermentation. In the fermentation process, a live organism metabolizes sugar to produce carbon dioxide, alcohol, acids, flavors, and water. The carbon dioxide expands the structure of the baked good. The other by-products play key roles in the development of flavor, odor, and texture. Traditionally, chemical leavening and yeast leavening have not been used in combination. Yeast performance during fermentation is pH dependent. It was believed that chemical leavening, which generally has neutral pH, would inhibit yeast

B. B. HEIDOLPH
The NutraSweet Kelco Company Food Phosphates A Unit of Monsanto Company St. Louis, Missouri

understanding of the mechanism of chemical leavening, as well as the tools, and a portfolio of available products.

THE MECHANISM
In general, leavening is considered to be a process whereby carbon dioxide is incorporated into a batter or dough and then expanded upon heating. The source of carbon dioxide can be from yeast fermentation or a chemical source. Beyond carbon dioxide, other gases playa role in the expansion of baked products. These other gases are sometimes overlooked but include ammonia gas (from ammonium bicarbonate or ammonium phosphates), water in the form of steam, and air that has been incorporated during the mixing process.

hemical leavening systems have been known since the first baking powder was formulated in 1838 in England (1). Sodium bicarbonate is believed to have been used as a source of carbon dioxide since the 14th century (1). Present-day formulation is both .a matter of art and science, Many times, formulation of a new product involves trial and error, Experimentation can be minimized with a clear
Publication no. W·1996-0308-01 F.
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1996 American Association of Cereal Chemists. Inc.

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MARCH 1996, VOL. 41, NO.3

ammonia gas. For chemical neutralization. When the batter or dough reaches this temperature. Table I. Potassium and ammonium bicarbonate can also be used in chemical neutralization. carbon dioxide is the primary source of leavening. The neutral salt formed will also impact the final product characteristics such as flavor. ammonium bicarbonate can be used in a variety of baked goods. AMCP. 52 159 33 40 145 45 93 80 80 GDL Lactic MCp·H2O AMCP AMCP Phos Acid Cream Tartar Propionic SAPP SALPA SALPH SAS Sorbic of sodium bicarbondate 83 172 45 115 100 104 70 n 100 Fig. textural characteristics. in many cases.O water dioxide Adipic acid Ascorbic acid Citric acid Dicalcium phosphate dihydrate Dimagnesium phosphate Fumaric acid Glucono delta lactone Lactic acid Monocalcium phosphate monohydrate Monocalcium phosphate anhydrous stabilized Monocalcium phosphate anhydrous Phosphoric acid Potassium acid tartrate Propionic acid Sodium acid pyrophosphate Sodium aluminum phosphate anhydrous Sodium aluminum phosphate 4 hydrate Sodium aluminum sulfate Sorbic acid • Neutralizing value defined as parts (by weight) weight) of leavening acid will neutralize. They found that when neutralized with a leavening acid. Neutralizing Baked Products Acid Source Va. Typical baked products include cookies and crackers. color. Chemical Leavening There are two basic types of chemical leavening=-decomposition and chemical neutralization. Generally. and the salt's impact on proteins. Moisture is related to cell structure. Water generated from the leavening reaction (Fig.HCO. crumb appearance. sodium bicarbonate is the "workhorse" of the industry. The rate at which carbon dioxide is released is associated with the rate at which the proton from the acid becomes available to react with the bicarbonate. For chemical neutralization. the sodium bicarbonate quickly solubilizes and is ready to react with the acid salt. DCPD. flour. Leavening by chemical neutralization. chemical leavening can provide a boost in the oven to compensate for loss of yeast activity over storage. pyrophosphate and sulfates can contribute an astringent flavor to finished products. Formulations that are tolerant to a range of temperature conditions. or only upon baking. including those with high moisture and volume. Por chemical leavening to be used in place of yeast fermentation. sodium aluminum phosphate. SAPP. and level of hydration. or fat.fermentation. Lajoie and Thomas reported research evaluating the use of ammonium bicarbonate in combination with leavening acids in a chemical neutralization process (3). and dimagnesium phosphate. and appearance. timing of release.lues for Acid Sources That Can Be Used in Chemically Abbreviation Adipic Ascorbic Citric DCPD DMP Fumaric: Leavened NV" 115 heat NH. sodium acid pyrophosphate. once the liquids have been added to a formulation. In general. MCP. This process is demonstrated in Figure 2. + ammonia CO. and carbon dioxide (Fig. there are a number of hurdles that need to be addressed including flavor. 2. presence of water-binding components such as starches and gums. For example. In combination. it can go directly from the mixer to the oven. In recent years. Fermentation requires considerable time for production of carbon dioxide. this leavening mechanism is used only in finished baked products that are low in moisture (less than 5%. that 100 parts (by CEREAL FOODS WORLD 1119 . In most cases. 1. 2) can eventually form steam. Ammonium salts can contribute an odor if they are not completely volatilized out of the product. The process where a bicarbonate source is neutralized by an acid is called chemical neutralization. Typically. Each leavening acid has its own distinct timing of release and rate of reaction. texture. Chemical leavening offers the ability for carbon dioxide release immediately. Holmes and Hoseney (2) reported in 1987 they did not see this pH inhibition of yeast function in their frozen dough systems. and moisture. waterbinding characteristics of the residual salt. dicalcium phosphate dihydrate. Organic acids can provide their own unique flavor characteristics. Decomposition. Decomposition of ammonium bicarbonate. the ammonium bicarbonate breaks down to water. GOL. anhydrous monocalcium phosphate. including the presence of divalent cations such as calcium. Chemical Neutralization. The moisture can vary from dry to gummy. odor. can be achieved. formulators have begun to utilize chemical leavening with yeast The advantages of chemical leavening can often compensate for some of the disadvantages of yeast. rarneters are critical to prevent the retention of ammonia gas and the off-flavor associated with it. Many formulators have begun to look for opportunities where chemical leavening and yeast leavening can be used in combination or where chemical leavening can be used in place of yeast fermentation. thermal decomposition is used in combination with other sources of leavening. SALP. sodium aluminum sulfate. thermal decomposition utilizes ammonium bicarbonate as the gas source. The classic example of decomposition is the use of ammonium bicarbonate. often less than 2%) and that have low volume. gluconodelta-lactone. concentration of sugar. DMP) or acidity from other components in the formulation-fruit. Some of these disadvantages are that yeast dies with time and is sensitive to temperature. Other formulation factors will also affect reaction rate. These pa- HX Acid Salt + NaHCO) Sodium Bicarbonate -----> NaX + Neutral Salt Water Carbon Dioxide Fig. The source of acidity can be a traditional leavening acid (monocalcium phosphate. Decomposition is dependent on the breakdown of the leavening agents in the presence of moisture or heat to provide the leavening gas to the system. The thermal decomposition temperature for ammonium bicarbonate is 59°C. There is no need to ferment or proof the product and. Crumb appearance can vary from fine to coarse depending on the salts that are used. All of these bypro ducts are capable of providing leavening gases that can expand during the baking process. + carbon H. including freezing. over time. ammonium bicarbonate -------> NH. SAS. The final color of the crumb can vary from white to creamy depending on the final pH. I). Chemical leavening is not a biological process.

Mep and AMCP have a pH around 6. AMCP.0-2. The ratio of acid and bicarbonate will impact the final product pH.0 Waffle mix • Based on percent of solrds. SALP. AMCP AMCP. higher temperatures and moisture levels will accelerate the rate of reaction.9. color.5. determine the leavening acid's NY value from the table. MCP.0 0. In this test. MCP. AMep. Leavening acids are sold based on a specified minimum neutralizing value. SAPP SALP. In general. SALP. an easy equation calculates the use level of the leavening acid as follows: first. DCPO. SALF. Mep. This provides a measure of difference in rates of reaction for a leavening system within a product formulation as expansion due to carbon dioxide formation. AMCP.25 Self-rising com meal Self -ris ing flo ur 1.25' 1. Fumaric. SAPP 28. calculate the use level of the leavening acid by multiplying the amount of baking soda by 100 and dividing that number by the neutralizing value.3 .25-1. SAPP 28.2. SAPP 28. SAFP.0 0. MCP. VOL 41. SALP. As much as 20% of the evolved gas can remain in a dissolved phase in the dough. Table II. which can affect the flavor and appearance of the product.5-2. more important.e. decide on the amount of soda to be neutralized by each acid.5-2. OMP DMP. OMP. a simple biscuit mix is placed in an airtight mixing bowl. and bakers or formulators can select the right product for their particular "critical zone. taste). NY is a guideline to assist in formulation work and not a hard and fast value. SAPP 28. the NY changes: for ammonium bicarbonate it changes by a factor of 0. SAPP 28. There is also a portion of dissolved carbon dioxide present in the dough. SALP. SALP. To determine the amount of leavening acid needed for a bakery product..5-2. if any. AMCP 40. SAPP 28 DMP.43. SAPP 40. In general. the formulator must first ascertain the baking soda level necessary for adequate leavening in the formulation. SAPP 28 28. MCP.6-1.1-7. SAPF 28. AMep. SAPP 28.5-2.5-2. The neutralizing values of some leavening acids when used with sodium bicarbonate are listed in Table I.e. SAPF 21. Note that an increase in temperature or stir time or addition of other ingredients will affect the final rate of reaction. SAPF 26. Different acids can buffer the pH of the baked product. Some ingredients can suppress the rate of reaction. AMCP.. AMCP.5-1. . AMCP.5-2. MCP. i. SAPP and DMP buffer around 7.5-2. Once this is known. SALP. This ensures sufficient acidity to neutralize the bicarbonate. SALP.0 1. The amount of gas evolved is converted to the percentage of total soda present and plotted against time. DCPD DMP. Then use that portion of the soda in the equation with the appropriate NY. DMP.5-1. The leavening acid or leavener and soda are generally used in such proportions so that after baking there remains little.0' 0. Mep. GDL OMP. SAPF SALP.8 Recommended Acid MCP.2 2. SAPP 26. Modifying the pH of a given bakery product can take large amounts of add or bicarbonate.0 1.0 0..1875.5 1. All leavening salts are affected by cations to some extent Note thai the soda blank evolves about 20% of the original carbon dioxide. As little as a 0. decide on the amount of baking soda in your bakery product (refer to Table 11 for starting guidelines). the difference in color is obvious." the point in the preparation process where gas release is desired. MCP.2' \.ing Value The concept of neutralizing value (NV) was developed to both compare the available acidity of various leaveners and. SAPP 40. SAL? SALP. and third. DCPO DMP. organic acidulants are the only acids that can be used for a final pH of less than 6. the pH may need to be adjusted after initial formulation work by changing the ratio of acid and bicarbonate. DMP OMP. The results provide a convenient yardstick for comparing the reactivities of different leavening acids. SALP.0 0. AMCP. These tests were conducted at 27°C with 3 min of stirring. SAPP 28. Figure 4 shows percent batter expansion versus time for batters containing AMCP.5-2. The dough rate of reaction (ORR) is used as a guide because it tests the reaction rates for leavening acids under controlled conditions.1 unit change in pH can cause a discernible color difference in baked products. which competes for water. SAPP 40. Adipic.5-2. The soda blank curve includes all of the ingredients minus the leavening acid. Cations such as calcium (from milk or added in the form of a calcium salt) will suppress the rate of reaction by interacting with the acid salts and preventing them from undergoing hydration or dissolution.0 1. unreacted soda or acid in the finished product. MCP. Adipic. SALP. Sugar.3-1. NO. It also illustrates the impact of reaction rate on practical aspects of baking such as batter volume and viscosity. suppresses the rate of reaction by as much as 5-10%. 120 I MARCH 1996. OMP OMP. sodium aluminum 1. AMCP. DMP SAPP 28. the acidulants may be adjusted to provide a target pH above or below neutral or to optimize other product characteristics.0 0. MCP. SALP. SAPP 28. SALP.2 pH units. MCP AMCP. SAPP SAPP 37. SAS AMCP. such as pancake batter. OMP. Fumaric. with potassium bicarbonate by a factor of 1.9375. The bowl is attached to a device that measures the gas evolution (COl)' Water is added to the biscuit mix and the mixture is stirred. Citric MCF.25-2.0 1. Neutralizing values are determined by a simple titration method (AACC Method 2-32A [4]). MCP. SALP. SALP. to permit the correct level of use. ocrn 21. sodium aluminum phosphate anhydrous (SALPA). SAPF 28. Fumaric. DMP AMCP. DMP 40. The neutralizing value has been defined as the parts by weight of sodium bicarbonate that 100 parts by weight of leavening acid will neutralize.0 0.ltrali:r. SAPP 28 OMP. MCP Cake mixes Angel Layer Co m Cookie mixes ffiU ffins/bread Crackers Frozen biscuit doughs Frozen cake batter Frozen pancake batter Hush puppy mix Muffins Panc-ake mixes Pizza mix Refrigerated dough Scone Batter Expansion Another means of evaluating reaction rate is to measure the expansion of batter. SALP. DMP AMCr. Figure 3 demonstrates the leavening rates of various leaveners as characterized by the DRR lest. SAPP21. AMCP. SALP. release all of the carbon dioxide. The DRR test is used to measure or predict the rate of carbon dioxide release during mixing and holding of a standard dough.0-2. Typically. SALP. SALP will buffer pH in the range of 7. When using more than one leavening acid.0-0. AMep. 6 Dough Rate of Reaction The select jon of a leavening acid is based on the timing (when carbon dioxide starts to be released) and rate of release (the speed at which the carbon dioxide is evolved) of carbon dioxide in the dough or batter mixture.3-7 . Chemically Leavened Baked Products=-Startlng Levels for Sodium Bicarbonate and Recommended Leavening Agents Product Baking powder Biscuit mix Breading batter mix Cake doughnut mix Percent Bicarbonate 30-40 1. Fumaric. At 0. SAPP 40. SAPP 28. Leavening acids with varying reaction rates are available.6-1.7 1. A calculation for each acid is necessary.TOOLS Ne!.5' 1. When using other sources of bicarbonate. DCPO. There are some exceptions to this balancing of leavener and soda when particular effects related to the pH of the final product are desired (i.7-2. Although NV is a convenient tool for some bakery products. AMCP. SAPP 26. second.

An example of how to use this chart would be to evaluate the leavening system of a cake formulated with Mep and SALP as the leavening acids. 80 70 c 60 . soda. Batter reaction rates for individual leavening acids are shown in Figure 5. Note that this figure provides a snapshot of what is going on in the baked product system. and DCPD. The batter also increases in viscosity because bubble surface tension force mimics solid particle properties. 4. The figure provides information on the time it takes to get 60% of the available carbon dioxide to be released at a specified temperature. has been known since the 14th century. after 12 min of baking (half the bake time) the batter temperature would be 40°C. The temperature vs. is the most commonly used member of the bicarbonate family. sodium bicarbonate is used without an acid source. The release AMCP SALPA SALPH OMP Leavening Agent cepc Fig. height. or ability to hold a batter.. OGPD = dicalclum phosphate dihydrate. In some products. also referred to as baking soda. An expanded batter thickens and its flow properties will change. When gas bubbles form in the batter. the' SAPP 28 cake would potentially have more volume-if indeed the batter sets up quickly enough to avoid deflation after lift by SAPP 28 because SAPP 28 begins to react earlier in the baking. simple biscuit mix).2 c 50 ~ c. time profile for a product can be determined by experimentation. which is determined at a single temperature using a biscuit dough formulation. LEAVENING AGENTS 80 Fine fumaric acid 70 MCP AMCP 7a . (Pancake batter at room temperature).. the batter expands. DMP. If the temperature remained constant. 40 30 20 10 0 Sodium Bicarbonate NaHCOj. Batter Rate of Reaction Batter reaction rates are determined at various temperatures using a batter formulation compared to the DRR. Sodium bicarbonate. CEREAL FOODS WO RLD 1121 . ~ (I) Be UJ m ~ c :! ftJ . C =' 15 min. during processing. it would take 200 min to complete the release of the remaining 60% carbon dioxide. m 40 <ll "0 SAPP 43 SAPP40 SAPP 37 > > W "0 0 N o Granular fumaric acid SAPP 28 SAPP 26 SALP SAPP 21 Soda blank DCPD Time (min) Fig. B = 10 min. as the batter temperature is constantly changing during baking. SALPH = sodium aluminum phosphate 4 hydrate. SAPP 28 was used along with the MCP to make the cake. This demonstrates that SAPP 28 begins to react sooner and faster than does SALP If the same formulation and bake scheme were selected for these two cakes. it would take approximately 40 min at a constant temperature of 40?C to release 60% 'of the carbon dioxide. Batter expansion expressed as a percentage increase versus the starting point.. and 0 = 30 min. SALPA '" sodium aluminum phosphate anhydrous. If instead. Batter expansion tests can be used to understand the release of carbon dioxide over time as well as the bench tolerance. Heat-activated leavening agents do not show significant expansion. Only the SALP would still be present in the cake to release additional carbon dioxide.phosphate 4 hydrate (SALPH). 3. and texture of the pancakes over time. AMCP '" anhydrous monocalcium phosphate. Batter expansion test. OMP = dimagnesium phosphate. A = 5 min. If the cake is baked at 177°C. This change will impact the diameter. Dough rate of reaction chart (3-min mix time at 27"C. such as cookies and crackers..!: 60 OJ 8 o 13 E Q) 0.

as without nuclei. brown spots can be observed on the surface of the baked product due to poor dissolution of the sodium bicarbonate-resulting in areas of localized alkalinity. carbon dioxide. and surface cracks. 119 parts of potassium bicarbonate are needed compared to 100 parts of sodium bicar- During baking. which occur later in the baking during the browning phase. Like potassium bicarbonate. along with the calcium phosphates. and flavor. adipic. crust color. Studies have demonstrated that equivalent sensory characteristics. 10 => II) c CD ::J C 2 CD 4 MCP 2. bonate. or sweetener. all products of the reaction shown in Figure 1 should be baked out of the product in theory. o :. are leavening acids that hydrate and undergo rapid dissolution. Granulation does not Significantly affect the overall rate of release of carbon dioxide. AMCP '" anhydrous monocalcium phosphate. During baking of high-moisture or high-volume products. volume. In many cases such as cookies. The versatility of the different bicarbonate sources is an area for further exploration. In research on cakes using ammonium bicarbonate neutralized with a leavening acid. it will affect the finished product characteristics including spread. low-volume products. If granulation is too large. It provides formulation flexibility. citric. Nucleating acids are important for structure and rapid early rise during initial heating. . the fact that ammonia gas (NH3) is also released on heating must be. It is sometimes used to reduce the sodium content of products. when ammonium bicarbonate is substituted completely or partially for sodium bicarbonate. or from thermal decomposition. When accounting for leavening power. To obtain equivalent leavening power. pH.. ammonium bicarbonate has not been used in chemical neutralization type leavening (Fig. Other finished product characteristics including pH. can be achieved when the bicarbonates are substituted for each other (5). however. Generally. Ammonium bicarbonate is typically used in low-moisture.3 . SAP? '" sodium acid pyrophosphate. spread. THE ACIDULANTS $! Q) lOO SAPP 28 a. Mechanical action from mixing also aids in the formation of nuclei for later carbon dioxide release. and moisture can be manipulated by incorporating potassium bicarbonate in place of or in combination with sodium bicarbonate in the formulation. MCP = monocalcium phosphate. without affecting the pH. 5. Thermal decomposition for sodium bicarbonate occurs late in the baking cycle at 109. In general. The bicarbonates provide an opportunity to manipulate finished product characteristics. Potassium Bicarbonate KHCOl has been used both alone as well as in combination with sodium bicarbonate. Larger granulation can provide shelf-life stability for dry mix products . 2). DCPD " dicalcium phosphate dihydrate.. o Ul E o c t5 ~ o o 60 40 rr:: CD m Leavening acids can be grouped into categories based on their release characteristics: nucleating agents are those that react with soda during mixing or in the bowl. MCP and AMCP. SALP " sodium aluminum phosphate.of the carbon dioxide can be due to acids present in other formulation ingredients. ?f2. Batter rates of reaction curves. NO. This role is critical. such as flour. VOL 41. factored into the formulation development. fruit.::::. handling. Nucleatin. 122! MARCH 1996. moisture. ammonium bicarbonate does not impact the final pH. the ammonia gas can be retained in the finished good. Because they react so quickly.5°C. Time until 60% of reaction versus batter temperature. and malic acids. height. and holding prior to baking and expansion. ammonium bicarbonate is selected in a formulation to provide additional leavening gas. These acids playa key role in determining the crumb structure and appearance by providing gas cell nuclei for. This research opens the possibility of using ammonium bicarbonate along with a leavening acid in applications where it has not previously been used. The substitution of 94 parts of ammonium bicarbonate for 100 parts of sodium bicarbonate provides equivalent level of carbon dioxide. fumaric. Ammonium Bicarbonate NH4HC03 was discovered to provide leavening gases about the same time as sodium bicarbonate. Because of this. including nutritional value. High pH favors the Maillard reactions. They quickly give up protons that react with the sodium bicarbonate and evolve carbon dioxide during mixing. nucleating acids are not used as the sole leavening acid in formulations. some of which are treated with flow conditioners. Sodium bicarbonate comes in a variety of granulations. it would take infinite pressure to form an air cell in a batter or dough system (6). Lajoie (5) was able to achieve acceptable finished product characteristics including cake height. height. time-released agents react after a period of time. lactic. volume. much of the carbon dioxide generated can be lost during forming.g Agents Organic acids such as tartaric or cream of tartar. and heat-activated agents do not react significantly in the bowl or during holding and are triggered by heat. including flavor. which is released later.5 E F 10 30 40 50 60 70 Batter Temperature (DC) Fig.

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