ADVERTISEMENT
2 /3 FREE ARTICLES LEFT THIS MONTH Remaining
Chemistry matters. Join us to get the news you need.

If you have an ACS member number, please enter it here so we can link this account to your membership. (optional)

ACS values your privacy. By submitting your information, you are gaining access to C&EN and subscribing to our weekly newsletter. We use the information you provide to make your reading experience better, and we will never sell your data to third party members.

ENJOY UNLIMITED ACCES TO C&EN

Profiles

Vladimir Ipatieff is the catalysis superhero you’ve never heard of

Russian-born scientist revolutionized chemistry by helping launch heterogeneous catalysis more than a century ago. Today, hardly anyone knows his name

by Mitch Jacoby
May 11, 2019 | APPEARED IN VOLUME 97, ISSUE 19

09719-feature2-ipatieffcxd.jpg
Credit: ACS Catal.
Vladimir Ipatieff, seen here shortly after arriving in the US in 1930, developed catalytic technology still used today.

The man looked over one shoulder, then the other, surreptitiously making sure no one was within earshot. Convinced the coast was clear, with a Russian accent, he said, “Ipatieff did the right thing to defect.”

Northwestern University’s Tobin J. Marks doesn’t recall the cautious man’s name, but he does remember that the Soviet chemist waited to catch Marks alone in a quiet corner at a Gordon Research Conference on catalysis in the early 1980s to share his thoughts. At the time, the Cold War was dragging on.

The man was referring to Vladimir Nikolayevich Ipatieff, the self-taught chemist who, in the early part of the 20th century, laid much of the groundwork for catalytic organic chemistry and petrochemical refining, cornerstones of today’s global chemical enterprise.

Born in Moscow just over 150 years ago, Ipatieff rose to prominence as a chemist during World War I. At the behest of Czar Nicholas II, he directed Russia’s chemical industry in the preparation of explosives and in other war efforts. But in 1930, as Joseph Stalin tightened his grip on Russia, the dreaded state police arrested numerous high-ranking officials and others who had been loyal to the czar and opposed communism. Several of Ipatieff’s friends and coworkers were executed. Others simply disappeared. Fearing for his life, Ipatieff fled and did not return, even after the turbulent times ended. Eventually he made his way to Chicago, where he led research programs at Universal Oil Products (UOP), a chemical engineering technology company, and at Northwestern.

Although he developed several industrial catalytic processes that are still used today, Ipatieff and his contributions have largely been forgotten outside hard-core catalysis circles. That’s regrettable, today’s catalysis practitioners say. Young scientists, they argue, can become more productive and better prepared for their careers by learning chemistry history, including stories like Ipatieff’s.

As a teen, Ipatieff attended military school in Saint Petersburg, focusing on math and artillery courses. He then began teaching those subjects and, according to his memoirs, used his spare time to study chemistry by reading textbooks by Dmitri Mendeleev and Nikolai Menshutkin. Ipatieff graduated in 1887 at age 20, becoming an officer in the czar’s army. His high marks in school earned him a small government bonus that he used to build a home laboratory, where he gained rudimentary hands-on experience in chemistry.

After serving as a field officer for 2 years, Ipatieff returned to the military academy in Saint Petersburg as an upper-level (or a graduate) student. That’s where he began investigating the properties of the steel being used to make artillery systems. That work led to his first research paper, published in an artillery journal in 1892, the same year he was appointed chemistry instructor at the academy. Ipatieff’s investigations of metals led to him developing steel chemical reactors for carrying out reactions of organic compounds. And this launched some of the work for which he is best known.

Around the turn of the century, Ipatieff made a seminal discovery: chemical reactions can be influenced by the walls of the container in which they’re taking place—like the inside walls of a steel reactor.

One case Ipatieff studied involved isoamyl alcohol. He found that flowing the alcohol through a heated iron tube stripped hydrogen off the end of the molecule, producing the corresponding aldehyde and molecular hydrogen. No reaction occurred when he used a quartz tube. Ipatieff determined that contact with the inside surface of the iron tube caused various types of alcohols—primary, secondary, and tertiary forms—to be dehydrogenated, forming aldehydes, ketones, and alkenes, respectively. He labeled these phenomena “contact reactions.” Today’s term is heterogeneous catalysis.

09719-feature2-fightercxd.jpg
Credit: Mitch Jacoby/C&EN
The Royal Air Force fleet of Hawker Hurricanes, including this one on display at the National Museum of the United States Air Force in Ohio, maintained air superiority over German fighter planes in World War II, thanks in part to catalytic processes Ipatieff developed for making ultra-high-octane fuels.

Recognizing that the surfaces of inorganic solids could stimulate organic reactions, Ipatieff went on to conduct systematic studies of metals and metal oxides, especially as catalysts for alcohol dehydration. He discovered that catalytic behavior—in particular, the effectiveness or efficiency of a catalyst—could be enhanced by finely dispersing catalyst particles on an inert support and by including small amounts of zinc or copper on the support. These kinds of additives, now referred to as promoters, are still used in industrial reactions today.

Several scientists, including some who knew Ipatieff personally and others who were born after he died in 1952, have written extensively about his contributions to chemistry. A recent example comes from Christopher P. Nicholas, who conducts catalysis research at UOP nearly 90 years after Ipatieff began working there (ACS Catal. 2018, DOI: 10.1021/acscatal.8b02310).

Ipatieff determined that γ-alumina, a type of aluminum oxide, functions as a highly effective dehydration catalyst, particularly for converting ethanol to ethylene. Nicholas notes that this ethanol-to-ethylene work later led Ipatieff to develop methods for converting ethanol to other alkenes, such as butadiene, a key material needed for manufacturing rubber. By the 1940s, these processes were used in the Soviet Union and the US for making hundreds of thousands of metric tons of butadiene annually. They are still used commercially.

One of Ipatieff’s biggest turn-of-the-century chemistry innovations was combining surface catalysis with high pressure. He did so through the development of specialized autoclaves, sometimes referred to as bombs. Ipatieff designed these steel vessels such that their tops and bottoms were rimmed with mating knife edges that could dig into a copper sealing ring when bolted together, allowing the containers to be sealed tightly and withstand extreme pressures.

As UOP’s Aristid V. Grosse noted in a 1937 tribute to Ipatieff, these metal test tubes introduced high pressures and high temperatures as new factors—meaning previously unexplored reaction variables—in chemistry research (J. Chem. Educ. 1937, DOI: 10.1021/ed014p553).

09719-feature2-scheme.jpg
Made by treating silica with phosphoric acid, the catalyst SPA was long used to make high-octane fuels via olefin oligomerization (top) and aromatic alkylation (bottom).

Using the autoclaves, which he sometimes lined with copper, silver, or other catalytic materials, Ipatieff explored chemistry at pressures nearly 500 times as high as atmospheric pressure and at 500 °C. Under these extreme conditions, which were unattainable to chemists using conventional glass equipment, Ipatieff made commodity chemicals and other high-volume products via synthetic routes that were potentially less expensive than conventional ones of the time. For example, he used his high-pressure methods to oxidize phosphorus to phosphoric acid, widely used for making fertilizers and detergents. He also showed that copper and other metals commonly used in manufacturing could be isolated from aqueous salt solutions, a simple alternative to metal refining. All these processes were—or still are—significant industrially.

“Ipatieff had a unique background in munitions, artillery, and metallurgy that led him to think about the properties of materials and how they influenced chemical reactions,” says Bruce C. Gates, a chemical engineer at the University of California, Davis. Ipatieff’s experience with military equipment provided the know-how to work at high temperatures and high pressures, setting him apart from other chemists, Gates adds. “Ipatieff recognized that he wasn’t limited to using glassware, which opened up a huge horizon of organic transformations that ultimately led to petroleum refining.”

Most of Ipatieff’s work in the field that was later dubbed petroleum refining took place in the US after 1930, when he emigrated from Russia. Shortly after coming to Chicago, he developed a highly active refining catalyst by treating silica with phosphoric acid. Known as “solid phosphoric acid,” or SPA, the acidic catalyst mediated the stringing together of butenes or a mixture of butenes and propene into short chains. When followed by hydrogenation, the process yielded gasoline with an octane rating of 81, far higher than the 65-octane-rated fuel produced at the multibillion-liter level in the US at that time. In general, the higher a fuel’s octane rating, the better an engine performs.

According to Nicholas, oil companies quickly commercialized Ipatieff’s process, building more than 100 refinery units from 1935 to 1945 to run this fuel-making chemistry. Nearly 10% of today’s refineries continue to make gasoline in this way, he says.

SPA was also used to make fuels with even higher octane ratings. For example, the catalyst was used to drive aromatic alkylations, such as the reaction of benzene with propene to make cumene (also known as isopropylbenzene), a key component of 100-octane aviation fuel. Initially, for reasons of national security, details of this refining process were kept out of the open literature, Nicholas points out. Eventually, the gag order was lifted, and Ipatieff and his longtime research associate, Herman Pines, a younger colleague with whom he worked at UOP and at Northwestern, became well known in chemistry circles for developing various acid-catalyzed processes that yielded ultra-high-performance fuels.

It’s important to learn the history of your field and appreciate how you stand on the shoulders of those who came before you.
Christopher P. Nicholas, catalysis chemist, UOP

Those methods were used during World War II to manufacture tens of millions of liters per month of 100-octane aviation fuels. These energy-rich mixtures are credited with giving Royal Air Force fighter planes a critical edge in terms of flying speed and maneuverability, enabling their significantly outnumbered pilots to maintain air superiority and repel the powerful German air force in the Battle of Britain, which began in the summer of 1940.

Ipatieff continued to work closely with Pines and other members of his research group developing industrial catalytic processes until his sudden death in 1952 at the age of 85. Ultimately, he left behind a 50-plus-year research legacy that includes nearly 350 journal papers and more than 200 patents. His name continues to live on, but only in a limited number of ways. For example, every 3 years the American Chemical Society (which publishes C&EN) awards the Ipatieff Prize for outstanding work in catalysis and high-pressure chemistry. And since 1953, Northwestern has appointed academics to the Ipatieff Professorship. Pines was the first person to hold that title. Marks is the current Ipatieff Professor. But other than those few honors, Ipatieff, despite having helped establish the vital-to-chemistry field of heterogeneous catalysis, has largely been forgotten. He was nominated 10 times for the Nobel Prize in Chemistry but never won.

“Ipatieff is certainly underappreciated,” Gates says. Part of the reason may be that he wrote in Russian, and his papers were translated and published in German, limiting their reach. And he filed very few patents before coming to the US. But in Gates’s view, Ipatieff’s lack of fame is also due to the fact that academic scientists typically don’t emphasize science history in their courses.

Should they? How would students benefit from learning about long-ago chemists?

09719-feture2-pinesipatieffcxd.jpg
Credit: Northwestern University
Herman Pines (left) and Vladimir Ipatieff developed catalytic methods for making high-performance fuels and other commercial products. (Note: Laboratory safety protocols were less stringent in 1948, when this photo was taken.)

“It would provide them with a unique perspective as to how important our field of chemistry was in the flow of history, politics, and major world events,” says Gabor A. Somorjai of the University of California, Berkeley. Somorjai acknowledges that he loves history but that not everyone does.

Spicing up a lecture with exciting historical tales can be like doing a cool pyrotechnics demo, Somorjai says. Both can go a long way toward sparking a student’s enthusiasm for science. That’s why he likes telling the Battle of Britain story when he teaches catalytic combustion kinetics.

Catalysis experts such as Somorjai who have worked in the field for many decades aren’t the only ones who see the benefit of teaching science history to students. Younger researchers also share the sentiment.

Nicholas, for example, says that one of the main reasons he wrote the ACS Catalysis paper was to address scientists’ striking lack of awareness of Ipatieff’s contributions. “It’s important to learn the history of your field and appreciate how you stand on the shoulders of those who came before you,” he says. “This history is very inspiring.”

Susannah L. Scott of the University of California, Santa Barbara, agrees. “It’s important to remind scientists, especially young ones, just how valuable people like Ipatieff are,” she says. Ipatieff came to the US under turbulent conditions and made discoveries that changed the trajectory of the entire US chemical industry, she asserts. Many of those discoveries and their long-lasting impact came from curiosity-generated research. Nowadays, because of budgets, goals, and deadlines, that approach to scientific discovery is rather uncommon.

“It’s curiosity that leads to the real breakthroughs,” Scott says. “We should admire that kind of curiosity and let it motivate us in our investigations.” She adds, “We should try to think like Ipatieff and encourage younger scientists to do the same.”

X

Article:

This article has been sent to the following recipient:

Comments
Siva Kesava Raju Chinthalapati (September 13, 2019 12:28 AM)
Dear Sir/Madam,

Can I get pdf copy of the article. He is inspiration for all chemists especially who work in petroleum industry.
Thanks C&EN for publishing article on catalysis super hero on whose footsteps modern petroleum industry is evolved.

Thanks and regards,
Siva Kesava Raju. CH.

Leave A Comment

*Required to comment