Psychological egoism claims that people do only act in their self-interest. Ethical egoism is the normative ethical stance that people ought to do what is in their self-interest. Although similar, the two beliefs are not compatible because ethical egoism, in order to be significant, must claim that people can be altruistic; otherwise it would make no sense to say that people should be selfish.
Neither philosophy is very good, though. Both have very big problems. A major problem with psychological egoism is that in order for a person to feel good about doing something (e.g. giving money to the needy) they must actually care about something other than themselves. They must care about what they do if doing that makes them feel good. But if they care about their deed, this contradicts psychologcial egoism which claims that people only care about themselves.
Ethical egoism is just obviously absurd. The only way that it is even remotely plausible is when altruistic moral assumptions are smuggled in and covered up. Ayn Rand is famous for doing this. She claimed that people should be selfish, but at the same time people should not violate others' rights. But respecting the rights of others when violating those rights could benefit you is an altruistic act. Another big problem is that egoism is the same as racism or sexism - it gives unjustified preference to certain beings. Racists give undue moral preference to their race, sexists to their sex, and egoists to themselves. All three violate basic moral ideas about fairness.
Psychological egoism is calculated in a way that is unattainable to prove or disprove. Because psychological egoists claim that evident acts of altruism are merely the acts of persons seeking a good feeling or adhering to social incentives to be seen to be altruistic; which also provides a "good feeling". Since this good feeling is unattainable, or at least improbable to identify, let alone determine, it is unworkable to prove that all people...
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