From your description, I think it could be a tinge of sibling rivalry. As you mentioned, she starts to act up when attention is focused on her younger sister. Plus at that age, it's alot about testing limits and boundaries so the tantrums are probably a mixture of both.
A friend of mine would get her son involved in getting his little sister ready -- help pick out her clothes or hold the milk bottle etc. This way, he learns that his sister needs the extra attention for now and by asking him to help, he is distracted and feels needed, thus lesser tantrums and screaming matches.
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