Alkalizing Cocoa and Matching the proper alkalized cocoa or liquor to the proper application is the key to a successful product.

Arlen Moser Blommer Chocolate Co.

hroughout history no time period has Coenraad recognized the darkening of the Thad a greater impact than the 19 th cen - color, giving it the appearance of a more tury on shaping the chocolate products of intense flavor. In general, the flavor was today. Rudolph developed the first enhanced through the smoothing out of the conche in 1879, which led to flavor improve - sour and bitter flavor undertones, creating ment of chocolate. Daniel Peter was the first the precursor for cocoa drinks today. person to successfully incorporate milk into Coenraad Van Houten patented his cocoa- chocolate in 1876 after many others had alkalizing discovery in Netherlands in 1828, tried and failed. In 1847, Joseph Fry added hence the phrases dutched cocoa or alka - additional into chocolate, giv - Arlen Moser has 30 lized cocoa are now used synonymously in years of experience in ing us the ability to form the chocolate bars today’s chocolate industry. Van Houten’s chocola te working for of today. In order for Joseph Fry to have patent ran out after 10 years and now the Blommer Chocolate. access to cocoa butter, Casparus Van cocoa and chocolate dutching method is used He began his career Houten developed and patented the cocoa in production and extensively in the food industry. Alkalized press in 1828. supervising the quality cocoa or chocolate can be found in drinks, Van Houten owned a factory in Nether - control department. ice cream and frozen treats, baked goods, He progressed into his lands which was producing cocoa drinks from pastry and compound coatings, as well as current position lead - ground cocoa beans. His chemist son, Coen - alkalized or dutched . ing research and raad, recognized that further improvements development for the Van Houten’s discovery is the basis for could be made to the cocoa. In 1828 he com - East Coa st operation. bined alkaline salts with cocoa powder, which this paper. Topics for discussion include alka - resulted in reduction of acidity (natural cocoa lizing cocoa and chocolate today, alkalized is typically 5.0 –6.0 pH). This reduced bit - chocolate and compound, as well as the appli - terness and sourness, making the drink more cation impact of alkalized cocoa. palatable. It also improved the dispersibility of cocoa powder in liquid. While the cocoa THE ALKALIZING PROCESS X butter content was significantly reduced from The process of alkalization can be broken the natural cocoa through pressing, its abil - down into three main categories: nib alka - ity to be incorporated into a drink still could lization, cocoa alkalization and choco - be improved, and was, through neutraliza - late liquor alkalization. Each process has tion. Color enhancement occurred as well. distinct advantages and disadvantages. ➤

The Manufacturing Confectioner • June 2015 31 Alkalizing Cocoa and Chocolate

Nib alkalization is Nib Alkalization Following the alkali reaction, roasting is the prevalent Nib alkalization (Figure 1) is the prevalent required. Depending on the roasting system alkalization method alkalization method across the United States and moisture content of the nib alkali mix, across the United and Europe because it offers advantages in some drying may be required before enter - ing the roaster. Roasting will complete the States and Europe coloring and flavoring not present in the other methods. Deeper and more intense drying process while enhancing chocolate because it offers reds are possible while offering a clean flavor. flavor. The time and temperature of the roast advantages in The first step of nib alkalization is car - will impact the final color and flavor in addi - coloring and ried out by fracturing raw cocoa beans then tion to the alkali reaction time. flavoring not removing the shell or skin. The remaining When the alkali reaction and roasting are present in the product is the cocoa nib or meat of the complete, the nibs are ground into choco - other methods. . The nibs are then soaked in an late liquor. The particle size is reduced (using alkali solution with additional moisture a ball mill or stone mill), the liquor is pressed added, possibly as high as 50 percent. The into cocoa cake and cocoa butter fractions, strength of the solution is predetermined then the cocoa cake is milled into a fine pow - by the desired pH and color of the end der. The red or dark powder is now com - product as well as the starting pH of the plete. It is also possible to eliminate the press - cocoa beans used. This alkali solution is ing step and use the alkalized liquor directly given time to penetrate and react with the in chocolate. cocoa nib. During this process, time and While flavor and color are positive attrib - temperature are controlled because longer utes of nib alkalization, there are also some time, higher temperature and basic pH con - negative aspects. Alkalizing the cocoa nibs ditions favor formation of more intensified also alkalizes the cocoa butter. Cocoa but - color due to degradation, Maillard ter processed with alkali can have increased reaction and anthocyanin polymerization. soaps, which if excessive, can soften the cocoa Aeration can be performed to further butter and impact the tempering if choco - enhance red notes through intensified oxi - late is its final use. The cocoa butter flavor dation of anthocyanins and other polyphe - can be altered and, depending on the degree nolic substances, either while under pres - of alkalization, the cocoa butter color can be sure or at normal atmosphere. Steam or impacted as well. This creates the need for air pressure could be added to hasten the pretreatment and deodorization of the cocoa darkening or browning effects depending butter, which results in yield loss. Because on system capabilities or desired outcome. of this cocoa butter yield loss and expensive Vacuum is also an atmospheric mechanism equipment required, nib-alkalized cocoa is used to manipulate color and enhance typically more costly than liquor-alkalized moisture reduction. cocoa or alkalized cocoa cake.

Nib Alkalization

Figure 1 ➤

32 June 2015 • The Manufacturing Confectioner Alkalizing Cocoa and Chocolate

Cocoa Cake Alkalization and not the cocoa butter. Not having alka - A positive factor Cake alkalization (Figure 2) is performed lized cocoa butter as a byproduct makes of cocoa cake with cocoa butter already pressed from the cake alkalization more economical and alkalization is the , usually down to 10 to could lead to a lower price. It also gives fact that only the nonbean roasters the opportunity to pro - 12 percent content. The roasting, win - cocoa is alkalized nowing, nib grinding into chocolate liquor duce alkalized cocoa. Negative factors and not the cocoa and pressing have already occurred when include limitations in color development butter. the cake alkalization takes place. and impact to flavor; flavors may be less Cake alkalization is typically performed pronounced or washed out as an already- on kibble (gravel-sized pieces of cocoa roasted cocoa is being reprocessed. Addi - ground from press cake) in a reaction ves - tionally, because kibbled cocoa cake is sel. Similar to nib-alkalized cocoa, the pH inconsistent in size, penetration of solu - of the natural cocoa will impact the fin - tion to each particle will vary. Particle size ished product. Also similar to nib alka - reduction in cake alkalization is also a lization, an alkali solution is added, time greater challenge than other alkalization and temperature will continue to be fac - methods. Through the wetting and then tors, and pressure and vacuum are also drying of the cocoa particles, agglomera - being applied depending on the desired tion occurs, creating the need for higher outcome. Aeration is applied as well in energy requirements for cocoa particle varying volumes to influence red notes in grinding than nib or liquor alkalization. addition to being used as a drying mecha - nism. The alkalized kibble will be dried to Chocolate Liquor Alkalization 5 percent moisture or lower and then Chocolate liquor alkalization (Figure 3) is milled into a finished cocoa powder. similar to cake-alkalized cocoa. It occurs A positive factor of cocoa cake alka - after roasting, winnowing and grinding into lization is that only the cocoa is alkalized chocolate liquor. As with other methods,

Cocoa Cake Alkalization

Figure 2

Chocolate Liquor Alkalization

Figure 3 ➤

The Manufacturing Confectioner • June 2015 33 Alkalizing Cocoa and Chocolate

Good- flavor the starting pH is a factor and an alkali product. Each will result in different fla - dutched cocoa or solution is required. Time and tempera - vors and functional attributes. Cocoa beans, chocolate cannot ture as well as atmospheric influences nibs, liquor or cocoa cake treated with affect the final product. There are limita - be derived from these alkali ingredients will be accompa - tions to moisture addition. Water addition nied by the statement Processed with alkali poor-quality beans to chocolate liquor makes it more viscous on an ingredient declaration label. and could be a and difficult to work with. Also, due to the product’s downfall density of the mass, aeration influences are Processing Variables Impacting the before the process limited in their impact, creating less color Finished Product is started. change. After the alkali reaction, moisture There are multiple processing variables removal is needed. This can be assisted capable of influencing the finished product with a thin film column evaporator and beyond the alkalizing agent used. may further enhance flavor development. Cocoa bean origin The substrate of the Pressing of the liquor (if being used for alkalizing process has a major impact. cocoa) and milling of the cocoa are needed Cocoa beans vary in flavor and color to complete the alkalized cocoa powder. throughout the world and crop quality A positive aspect of chocolate liquor varies due to weather influences. Good alkalization is that noncocoa-bean proces - flavor dutched cocoa or chocolate cannot sors are able to perform liquor alkaliza - be derived from poor quality beans and tion and it can be performed with limited could be a product’s downfall before the equipment. The negative is that the cocoa process is started. Color of the cocoa bean butter is alkalized, similar to nib alkaliza - is important for powders. If a finished prod - tion, resulting in further processing of the uct of deep red cocoa is desired, it cannot cocoa butter and additional expense. There be achieved unless some of the color is are color limitations as well. Because of inherent in the bean. the density, and inability to use moisture at high rates, deep reds are difficult to achieve pH The pH impacts flavor and color. This and darker brown is usually the result. includes the starting pH of the beans (between 5.0 and 6.0) as well as the amount Alkalizing Ingredients and type of alkali used. High pH is associ - The alkalizing ingredients shown in Fig - ated with darker colors. ure 4 can be used in alkalizing cacao. The Time/temperature Reaction temperatures limiting quantity is for each 100 parts of for red cocoas will typically be in the 75° to cacao nibs; the total quantity of alkalizing 85°C range and browns and blacks will be ingredients used is not greater in neutral - in the 95° to 125°C range depending on izing value than three parts by weight of desired color and equipment capabilities. carbonate. Holding cocoa at high temperatures for Varying rates of these alkali ingredients extended periods of time will influence can be used to achieve the desired cocoa color and flavor and if held too long will eventually damage the flavor. Alkalizing Ingredients Used in Alkalizing Cacao Moisture The amount of water used in the CFR-Code of Federal Regulations Sec. 163.110-114 reaction can accelerate color formation Potassium Sodium Ammonium and enhance red notes. Moisture between Carbonate K2CO 3 Na 2CO 3 (NH 4)2CO 3 MgCO 3 20 to 50 percent can be used if the process Bicarbonate KHCO 3 NaHCO 3 NH 4CO 3 Hydroxide KOH NaOH NH 4OH equipment is capable and the moisture in Oxide MgO the bean should be accounted for as well. Figure 4 High moisture will assist in achieving red ➤

34 June 2015 • The Manufacturing Confectioner Alkalizing Cocoa and Chocolate notes but it should be noted that the water when compared to an identical nonalka - Nonalkalized must be evaporated and may require lized formula. This presents some oppor - chocolate liquor extended drying or roasting time, affect - tunities. Boxed chocolates tend to display will be more acidic ing the flavor. multiple, noticeably different dark choco - and bitter while a lates in the same box, differentiating each Oxidation Air quality and quantity will dutched liquor or piece. The darker color may be a perfect accelerate the alkalizing process. Aeration cocoa properly of the cocoa with high volumes of air for application for the finished good. While it alkalized to a an extended period of time will enhance is less prevalent, alkalized liquor or cocoa neutral pH will red notes. can be used in as well. The liquor percentage of the chocolate have a less Atmosphere Air pressure or steam pressure recipe can be completely alkalized or astringent will accelerate the browning of the cocoa added as a blend of alkalized and nonal - profile. and assists when producing black cocoa. kalized chocolate liquor depending on the Steam pressure can also be used to acceler - flavor desired. Additionally, alkalized cocoa ate nib penetration with the alkali solution. can be added as an ingredient in choco - It should be noted that excessive pressure or agitation may cause the cocoa butter to dif - late to supply the dutched flavor. fuse to the surface of the nibs, causing flowa - Alkalized Cocoa in Compound bility and manufacturing issues. Vacuum can Coating be used as a tool as well but is typically used Cocoa compound coating is an alternative in the drying process. to milk or and the added ALKALIZED CHOCOLATE AND COCOA cocoa powder is the main flavor-driving COMPOUND XXXXXXXXXXXXXXXXXXX ingredient. Compound offers the advan - According to Mintel Group there have tage of a coating with multiple meltpoints been more than 100 new launches of which can offer new product possibilities as chocolate and compound products con - well as the ability to supply products in taining alkalized liquor or cocoa over the warmer climates. The chocolate flavor is last three years. This is in addition to many driven by the type and quantity of the alka - of the fine alkalized chocolate products lized and nonalkalized cocoa powder. already on the market. Cocoa powder is the main color driver as Adding alkalized liquor into chocolate well. If strong cocoa flavor is not a require - can have positive influences on the finished ment for the finished product, there may be product. Nonalkalized chocolate liquor will opportunities to use darker alkalized pow - be more acidic and bitter while a dutched der in a lower dosage to produce the same liquor or cocoa properly alkalized to a neu - color. This can present a quality improve - tral pH will have a less astringent taste pro - ment and possible cost savings. While the file. This gives a producer an opportunity to cocoa butter has been pressed from the produce more than one flavor from the same liquor, 10 to 12 percent cocoa butter still bean type. The dutched flavor may pair more remains in the cocoa. Cocoa butter in high- favorably with a shell-moulded or enrobed enough quantities paired with the added center, providing a superior flavor experi - lauric fat in compound will create a eutec - ence. Alkalized liquor or cocoa as an ingre - tic effect. This is good for softening a dient in chocolate may also present the pro - chocolate center but is damaging to the ducer with the opportunity to reduce shine and shelf life of a coating. Alkalized time because many of the volatiles liquor is a possible ingredient for a filling have already been removed. or center but is not an ingredient for a Color of an alkalized chocolate is darker compound coating for this reason. ➤

The Manufacturing Confectioner • June 2015 35 Alkalizing Cocoa and Chocolate

If strong cocoa APPLICATION IMPACT OF ALKALIZED allow for sediment to collect on the bot - flavor is not a COCOA POWDER XXXXXXXXXXXXXXXX tom of the container over time. The fat requirement for the FDA description of cocoa powder is: content is also a hindering factor in blend - finished product, the food prepared by pulverizing the remain - ing cocoa into a water-based drink. Emul - ing material after part of the cacao fat has sifiers such as are needed to reduce there may be been removed from ground cacao nibs. the surface tension between the fat-loving opportunities to Optional alkali ingredients also specified and water-loving molecules. Thickeners, use darker and limited in CFR 163.110 (b) (1) may be used in preparation of cocoa. Cocoa such as carrageenan, are used to help keep alkalized powder powder will be less than 24 percent fat, the in suspension longer. in a lower dosage falling under the designations high-fat (break - to produce the fast cocoa), medium-fat (10 – 22%) or low- fat cocoa (<10%) whether alkalized or non - Final impact prediction of alkalized cocoa same color. alkalized. powder on a can be difficult as well. Evaluating the ideal cocoa powder can Type of dutched cocoa and the dosage used be a difficult task as the final result is not are obvious factors influencing the final always predictable. To evaluate cocoa flavor and color of the dessert. But, the impact properly, putting the cocoa in an other ingredients play a role as well. For application is always necessary to exam - instance, the addition of a nonfat milk pow - ine the cocoa’s true intrinsic color. Early der may have a lightening effect on the indicators such as extrinsic color can be final product color as well as muting some misleading. For instance, 22 to 24 percent cocoa notes. Conversely, the addition of fat cocoa powder (breakfast cocoa) and a more fat to the recipe in the form of but - 10 to 12 percent fat cocoa powder alka - ter and margarine could have a darkening lized to the same pH under the same effect. If heat treatment of the dessert is parameters will appear different. The 22 to required, color and flavor will be impacted 24 percent powder will appear darker in as well. Air content plays a role in the color color, giving the impression of stronger fla - and flavor of a whipped or foam-forming vor and greater coloring impact. This will dessert. Greater air content will lighten not be the case due to the fact that the color and reduce flavor impact. A greater 10 to 12 percent powder will have more dosage of cocoa may be required to deliver cocoa solids and greater flavoring and col - the chocolate impact desired. oring capability when used at the same Ice cream is an ideal application for rate. Other parameters such as moisture alkalized cocoa and, behind vanilla, choco - content and cocoa temperature can be mis - late ice cream is the second-most popular leading in extrinsic observation. flavor. Similar to whipped desserts, the Cocoa Drinks incorporation of air affects color and flavor Cocoa drinks, whether hot or cold, often impact. with high contain a lightly alkalized cocoa powder. overrun will appear lighter compared to The smoother taste with lowered bitter the same recipe with reduced overrun. An notes appears to appeal to the masses. increased dosage or a darker cocoa may Besides flavor and an attractive reddish- be required if high overrun is a require - brown color, an alkalized cocoa offers ment to meet color standards. High over - greater dispersibility over a nonalkalized run reduces cocoa flavor as well as the fact cocoa. However, while cocoa dispersion is that ice cream is a frozen treat. Low tem - greater in the dutched cocoa, it is not com - peratures desensitize the taste buds, cre - pletely soluble. The cocoa will be initially ating a need for higher flavor impact deliv - dispersed in a milk or water drink but will ered by a larger alkalized-cocoa dosage. ➤

36 June 2015 • The Manufacturing Confectioner Alkalizing Cocoa and Chocolate

Nothing can be more disappointing than reduced blood pressure and many other Nothing can be looking at a rich-appearing chocolate treat, potential improvements. more disappointing biting into it and finding out that it doesn’t refer to a broad class of than looking at a deliver the expected flavor. compounds found in all plants. The rich-appearing category contains many sub - Baked Goods chocolate treat, groups including , which break biting into it and and pastry are consumed down into many other subgroups including and enjoyed worldwide. Cocoa powder is flavanols, which in turn have subgroups of finding out that it typically the flavor and color driver and, their own. For the purpose of this paper, doesn’t deliver the like whipped and cooked desserts, color the concentration will be on flavanols. expected flavor. and flavor of the final product are difficult It is widely suspected that alkalizing of to predict. Experimentation on type of cocoa and chocolate will have negative cocoa and dosage used will be required effects on flavanol content. As discussed when developing a new product to achieve previously, there are many components to the ideal visual and sensory experience. alkalization, including the extent to which Any type and color of cocoa can be added the cocoa or chocolate is alkalized. The but close attention should be paid to the Hershey Center for Health and Nutrition pH of the cocoa used as well as the leav - performed a flavanol-content study on 20 ening agent. Natural cocoa is typically a commercial cocoa powders from seven dif - 5.6 pH but can range as low as 5.0 pH. ferent companies. The cocoa powders var - Alkalized red cocoas are typically in the ied in range from nonalkalized to moder - 6.8 to 7.8 pH range, while black cocoa ately alkalized with the gauge being the ranges from 7.8 to 8.6 pH. A cake recipe extractable pH. The pH range was pH 5.39 with natural cocoa powder and possibly for the most acidic to pH 8.06 for the most other acidic ingredients, such as Greek alkaline. The 20 commercial cocoas were yogurt, buttermilk or sour cream, will require baking soda as the leavening agent arranged into four categories: nonalkalized, since the baking soda is acid activated. An pH 5.39 to 5.76; lightly alkalized, pH 6.77 to alkalized cocoa with a pH greater than 7.0 7.13; moderately alkalized, pH 7.21 to 7.52; will require baking powder for leavening and heavily alkalized, pH 7.69 to 8.06. The since there is not sufficient acid to activate fat was extracted and testing was performed baking soda. Proper experimentation with to establish total flavanol content. new recipes should be performed as too Total Flavanols versus pH little or too much leavening agent will have As indicated by the chart in Figure 5, the negative implications on leavening (rise) or total flavanol content had an inverse rela - flavor (metallic or bitter). tionship with the pH value. When the pH Flavanol Impact increased, the flavanol content decreased. It would be remiss not to discuss polyphe - In the case of the heavily alkalized cocoa, nol and flavanol impact in this day and age it decreased substantially, but still had fla - since the cocoa and chocolate industry is vanol content remaining. Even though receiving a substantial amount of positive there were losses, the average flavanol con - press f or high polyphenol and flavanol con - tent of the lightly alkalized cocoa 13.8 tent. Polyphenols and one of its subgroups, (mg/g) and the medium-alkalized cocoa flavanols, are known for antioxidant activ - 7.8 (mg/g) would still remain in the top ity and many health benefits including 10 percent of measured foods with improved cardiovascular health, reduced detectable flavanols in the USDA data - oxidative effects of ldl , base. Alkalization appears to have a neg - ➤

The Manufacturing Confectioner • June 2015 37 Alkalizing Cocoa and Chocolate

Alkalization ative effect on flavanols but cocoa health comes at a higher cost of production and appears to have a benefits are still significant. higher cost to the consumer. Cake alka - negative effect on While this was a comprehensive study lization is usually less complicated to pro - of the relationship of pH and flavanols, duce and has no impact on the cocoa but - flavanols but cocoa many questions remain unanswered. Not ter, but it has color limitations as well as health benefits are mentioned in the study were alkalizing reduced flavor. Chocolate liquor alkaliza - still significant. agent used, type of alkalization process tion requires less equipment to produce (nib, cake, liquor), roasting times, bean ori - but has color limitations and can nega - gin, fermentation levels, flavanol load prior tively affect the cocoa butter. Matching to alkalization, etc. These and many other the proper alkalized cocoa or liquor to the factors affect flavanol content in cocoa and proper application is the key to a success - chocolate beyond the alkalization process. ful product. n

CONCLUSION REFERENCES Alkalizing cocoa and chocolate has been Beranbaum, Rose Levy, Maria Guarnaschelli, applied and enjoyed for the past 187 years. Vincent Lee, and Manuela Paul. Under - standing . The Cake Bible . New York: Through the process, consumers have been W. Morrow, 1988. Pp 473 –77. Print. able to enjoy dutched chocolates with their http://humantouchofchemistry.com/coenraad-johannes- reduced bitter flavor and intensified color. van-houten-discovery-of-cocoa-powder.htm Alkalized cocoa powders are now enjoyed in http://exhibits.mannlib.cornell.edu/chocolate/houten.ph p many colors, with distinctly improved fla - Li, Yue, Song Zhu, Yun Feng, Feifel Xu, Jiango vors and in some cases used where a natural Ma, and Fang Zhong. Influence of Alkaliza - cocoa just wouldn’t be a good application. tion Treatment on Color Quality and Total Compound coatings have been possible since Phenolic and Anthocyanin Contents in Cocoa Powder. Food Science and Biotech - the invention of the cocoa press, but the abil - nology 23.1: 59 –63, 2014. ity to use alkalized cocoa greatly expands Miller, Kenneth B., William J. Hurst, Mark J. the color and flavor possibilities. Payne, David A. Stuart, Joan Apgar, Daniel S. Alkalized cocoa and chocolate liquor is Sweigart, and Boxin Ou. Impact of Alkaliza - typically produced through three differ - tion on the Antioxidant and Flavanol Con - tent of Commercial Cocoa Powders” Journal ent methods: nib alkalization, cocoa cake of Agriculture and Food Chemistry 56 th ser. J. alkalization and liquor alkalization. They Agric.Food Chem Pp8527 –533, 2008. have advantages and disadvantages for the United States. Food and Drug Administration. suppliers and the users of these products. Department of Human Health and Services. Code of Federal Regulations Title 21. Vol. Nib alkalization offers the greatest range Part 163., 2014. Print. Cacao Products. of color and usually the finest flavor, but it Zijderveld, J. A. Cocoa Mass, Cocoa Butter, and Cocoa Powder. Industrial Chocolate Manu - facture and Use . By E. H. Meursing. Third Total Flavanols versus pH ed. London: Blackwell Science, 1999. Pp 101 – 14. Print.

Figure 5 Hershey Center for Health and Nutrition Presented at the PMCA Production Conference

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