In most cases whiskey continued as the sole anesthetic. It is estimated that both the North and the South used ether and chloroform some 125,000 times during the war despite Northern blockades that limited access to the South. However, this pales in comparison to the 476,000 wounded and 620,000 dead.
Chloroform was the method of choice. This was because "chloroform is faster-acting, non-explosive, and less likely to cause initial excitement and a flailing of limbs." This statement by Albin suggests there may have been preferential treatment depending on the rank of the patient: "...the science of anesthesiology has come far since those days when a general got a few drops of chloroform and a private was lauded for his spunk."
An offshoot of the use of anesthetics in the Civil War was the introduction of the nurse anesthetist. Catherine Lawrence was the first nurse to administer anesthesia on the battlefield during the second Battle of Bull Run near Washington, D.C.
References and Additional Reading:
http://www.uab.edu/medicine/news/latest/item/282-he-s-pretty-spunky-anesthesia-comes-of-age-during-the-civil-war
http://www.general-anaesthesia.com/images/civil-war.html
http://www.aana.com/aboutus/Pages/Answering-the-Call-Video.aspx
http://mentalfloss.com/article/31326/5-medical-innovations-civil-war
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